Multiphoton Upconversion Research Articles

Ultraviolet and White Light Emissions from Multiphoton Upconversion Transitions in Yb/Tm/Ho Codoped Cubic Zirconia Single Crystals Excited by NIR

Ultraviolet and White Light Emissions from Multiphoton Upconversion Transitions in Yb/Tm/Ho Codoped Cubic Zirconia Single Crystals Excited by NIR

Spatiotemporal control of photochromic upconversion through interfacial energy transfer

Dynamic control of multi-photon upconversion with rich and tunable emission colors is stimulating extensive interest in both fundamental research and frontier applications of lanthanide based materials. However, manipulating photochromic upconversion towards color-switchable emissions of a single lanthanide emitter is still challenging. Here, we report a conceptual model to realize the spatiotemporal control of upconversion dynamics and photochromic evolution of Er3+ through interfacial energy transfer (IET) in a core-shell nanostructure. The design of Yb sublattice sensitization interlayer, instead of regular Yb3+ doping, is able to raise the absorption capability of excitation energy and enhance the upconversion. We find that a nanoscale spatial manipulation of interfacial interactions between Er and Yb sublattices can further contribute to upconversion. Moreover, the red/green color-switchable upconversion of Er3+ is achieved through using the temporal modulation ways of non-steady-state excitation and time-gating technique. Our results allow for versatile designs and dynamic management of emission colors from luminescent materials and provide more chances for their frontier photonic applications such as optical anti-counterfeiting and speed monitoring.

Differences of up-conversion and temperature sensing behaviors of NaYF4: 2 mol % Er3+, 20 mol % Yb3+ Phosphors with cubic and hexagonal phases

In this work, NaYF4: 2 mol % Er3+, 20 mol % Yb3+ phosphors with cubic and hexagonal phases were prepared by co-precipitation method with different reaction temperature. The multi-photon up-conversion processes and optical temperature sensing properties are discussed. The emission spectra of hexagonal phase show higher emission intensity and lower red-to-green ratio (R/G), which are attributed to the decrease of local symmetric. And the number of photons (n), participated in the up-conversion processes, declines as the phase changes from cubic to hexagonal. This can be originated to the exhaustion of electrons on ground state level: 4I15/2 in hexagonal phase. And the fitting n of green emissions decline more obviously than red emission with temperature increasing. The temperature dependent FIR is fitted and the fitted function implies that the energy gap ∆E increases as the phase changes to hexagonal. And the max relative sensitivity reaches 0.012 K−1 at 300 K. Thus, NaYF4: 2 mol % Er3+, 20 mol % Yb3+ phosphors with hexagonal phase have higher SR and can be promising in FIR-based temperature sensing.

On-Chip Mirror Enhanced Multiphoton Upconversion Super-Resolution Microscopy

Multiphoton upconversion super-resolution microscopy (MPUM) is a promising imaging modality, which can provide increased resolution and penetration depth by using nonlinear near-infrared emission light through the so-called transparent biological window. However, a high excitation power is needed to achieve emission saturation, which increases phototoxicity. Here, we present an approach to realize the nonlinear saturation emission under a low excitation power by a simply designed on-chip mirror. The interference of the local electromagnetic field can easily confine the point spread function to a specific area to increase the excitation efficiency, which enables emission saturation under a lower excitation power. With no additional complexity, the mirror assists to decrease the excitation power by 10-fold and facilities the achievement of a lateral resolution around 35 nm, 1/28th of the excitation wavelength, in imaging of a single nanoparticle on-chip. This method offers a simple solution for super-resolution enhancement by a predesigned on-chip device.

Tetracycline Removal through the Synergy of Catalysis and Photocatalysis by Novel NaYF4:Yb,Tm@TiO2-Acetylacetone Hybrid Core-Shell Structures.

Novel hybrid core-shell structures, in which up-converting (UC) NaYF4:Yb,Tm core converts near-infrared (NIR) to visible (Vis) light via multiphoton up-conversion processes, while anatase TiO2-acetylacetonate (TiO2-Acac) shell ensures absorption of the Vis light through direct injection of excited electrons from the highest-occupied-molecular-orbital (HOMO) of Acac into the TiO2 conduction band (CB), were successfully synthesized by a two-step wet chemical route. Synthesized NaYF4:Yb,Tm@TiO2-Acac powders were characterized by X-ray powder diffraction, thermogravimetric analysis, scanning and transmission electron microscopy, diffuse-reflectance spectroscopy, Fourier transform infrared spectroscopy, and photoluminescence emission measurement. Tetracycline, as a model drug, was used to investigate the photocatalytic efficiencies of the core-shell structures under irradiation of reduced power Vis and NIR spectra. It was shown that the removal of tetracycline is accompanied by the formation of intermediates, which formed immediately after bringing the drug into contact with the novel hybrid core-shell structures. As a result, ~80% of tetracycline is removed from the solution after 6 h.

Superenhancement Photon Upconversion Nanoparticles for Photoactivated Nanocryometer

Highly doped lanthanide luminescent nanoparticles exhibit unique optical properties, providing exciting opportunities for many ground-breaking applications, such as super-resolution microscopy, deep-tissue bioimaging, confidentiality, and anticounterfeiting. However, the concentration-quenching effect compromises their luminescence efficiency/brightness, hindering their wide range of applications. Herein, we developed a low-temperature suppression cross-relaxation strategy, which drastically enhanced upconversion luminescence (up to 2150-fold of green emission) in Er3+-rich nanosystems. The cryogenic field opens the energy transport channel of Er3+ multiphoton upconversion by further suppressing phonon-assisted cross-relaxation. Our results provide direct evidence for understanding the energy loss mechanism of photon upconversion, deepening a fundamental understanding of the upconversion process in highly doped nanosystems. Furthermore, it also suggests the potential applications of upconversion nanoparticles for extreme ambient-temperature detection and anticounterfeiting.

Multi-shell structured nanocarriers with enhanced multiphoton upconversion luminescence efficiency for NIR-mediated targeted photodynamic therapy

Recently, upconversion nanoparticle (UCNP)-based photodynamic therapy (PDT) has attracted attention as an anticancer treatment that can address the limitations of light penetration depth to activate commercial photosensitizers (PSs) using the upconversion luminescence (UCL) process. However, the low UCL intensity of UCNPs and the overheating effect by the 980 nm NIR laser significantly reduced the therapeutic efficacy. To overcome these problems, it is essential to form UCNP with a multi-shell structure by varying the feed composition of Yb3+, which can improve the UCL intensity. To generate highly efficient theranostic systems, we prepared a multi-shell structured UCNP (UCNC60S3) system with enhanced UCL efficiency in this study that can activate two types of PSs with one laser irradiation and have tumor targeting properties. UCNC60S3 capable of emitting multiple wavelengths with enhanced photoluminescence efficiency (PL) were synthesized by a thermal decomposition method with two kinds of activators in a single nanoparticle. The UCNC60S3 with a multi-shell structure showed 267.6 and 387.3 fold enhancements in UCL efficiency than the core UCNP at wavelengths of 545 nm and 660 nm, respectively. In addition, multi-shell structured UCNPs combined with dual PS and tumor-targeted ligands (F-UCNC60S3-RC) exhibited a significant improvement in the therapeutic effect on cancer cells by near-infrared (NIR) irradiation. When an 808 nm laser at 2 W/cm2 intensity was irradiated for 5 min, F-UCNC60S3-RC showed 10 times higher phototoxicity to cancer cells than free PS. Therefore, the NIR-induced F-UCNC60S3-RC nanocarriers with a multi-shell structure and dual PS binding will be able to provide multiple emissions for bio-imaging as well as improved targeted cancer therapy.

Up-to-Five-Photon Upconversion from Near-Infrared to Ultraviolet Luminescence Coupled to Aluminum Plasmonic Lattices.

The incorporation of upconversion luminescence (UCL) materials into various plasmonic structures promotes light-matter interactions in nanophotonic systems. It has been experimentally demonstrated that UCL enhancement entailing two photons exhibits a quadratic dependence on the excitation intensity. However, in the field of plasmonics, there have not been sufficient studies on high-order multi-photon upconversion processes. We report up-to-five-photon UCL, wherein λ = 1550 nm near-infrared light is converted to 382 nm ultraviolet light, from core-inert shell nanoparticles coupled to aluminum plasmonic lattices. The five-photon UCL intensity of nanoparticles on the plasmonic lattice is over 800 times stronger than that on the flat glass. We demonstrate that the enhancement of UCL scales with the nth power of the local field enhancement for n-photon process. These findings give a strategy to obtain high-order multi-photon UPL with aluminum plasmonic nanostructures and can contribute to anti-counterfeiting application.

Near-infrared light responsive intensified multiphoton ultraviolet upconversion in nanostructures towards efficient reactive oxygen species generation.

Near-infrared-to-ultraviolet (NIR-to-UV) multiphoton upconversion has recently received increasing attention owing to its promising frontier applications in the fields of biomedicine and nanophotonics. However, the realization of high-efficiency NIR-to-UV upconversion remains a dispiriting challenge due to weak excitation light harvesting and photo-conversion efficiency. Herein, we propose a mechanistic strategy to achieve intensified UV upconversion by manipulating the injected excitation energy flux. A simple LiYbF4:Tm@LiYF4 host-sensitized sublattice core-shell nanostructure was initially proposed to compete with the concentration quenching effect and increase energy transfer efficiency. Then, the organic dye ICG was further coated to introduce the antenna sensitization effect to highly increase the absorption ability of nanocrystals. After optimizing the ICG number loaded on the surface and separation distance, up to 167-fold UV upconversion emission enhancement was achieved under low-power excitation of 808 nm. More importantly, the efficient UV upconversion exhibits enhanced reactive oxygen species (ROS) generation activity by fabricating a TiO2-modified upconversion nanocomposite, revealing great application potential in frontier fields such as in vivo photodynamic therapy and bioimaging-guided therapeutics. Our results can provide versatile designs to achieve efficient UV upconversion, overcome conventional limitations, and offer exciting opportunities for potential applications in biomedical fields.

Four- and five-photon upconversion lasing from rare earth elements under continuous-wave pump and room temperature.

Benefited from abundant long-lived intermediate energy levels of rear earth elements, large anti-Stokes lasing can be realized by multi-photon upconversion processes, which does not demand rigorous phase match and ultrahigh pump power. Here, we have fabricated an Er-doped silica microsphere with an ultrahigh intrinsic quality factor of 1.2 × 108. By continuous-wave (CW) excitation at 1535nm, four- and five-photon upconversion lasers are achieved simultaneously under room temperature, in which the lasing thresholds are estimated as 176 and 600μW, respectively. Beside the ultralow thresholds, the microlaser also exhibits good stability of lasing intensity for practical applications. The four- and five-photon upconversion lasing from rare earth elements have not been separately demonstrated under CW pump and room temperature until this work. This demonstration provides a prospect to realizing high-performance short-wavelength laser by pumping low-energy photons.

Manipulating the Injected Energy Flux via Host-Sensitized Nanostructure for Improving Multiphoton Upconversion Luminescence of Tm3.

Combating the concentration quenching effect by increasing the concentration of sensitized rare-earth ions in rational design upconversion nanostructure will make it easier to utilize injection energy flux and transfer it to emitters, resulting in improved upconversion luminescence (UCL). We proposed a host-sensitized nanostructure (active core@luminescent shell@inert shell) to improve multiphoton UCL of Tm3+ based on the LiLnF4 host. Yb3+ ions were isolated in the core as energy absorbents, and Tm3+ was doped in the interior LiYbF4 host shell. Compared with sandwich structured nanocrystals (Y@Y:Yb/Tm@Y), reverse structure (YbTm@Yb@Y), and fully doped structure (YbTm@YbTm@Y), the proposed structure achieved the highest efficiency of multiphoton UCL and favored a better FRET-based application performance as the Tm3+ located at an optimized spatial distribution. Furthermore, steady-state and dynamic analysis results demonstrate that by manipulating the spatial distribution of the active ions, excited energy can be tuned to enable multiphoton upconversion enhancement, overcoming the conventional limitations.

Intensifying Upconverted Ultraviolet Emission towards Efficient Reactive Oxygen Species Generation.

Multiphoton upconversion that can convert near-infrared irradiation into ultraviolet emission offers many unique opportunities for photocatalysis and phototherapy. However, the high-lying excited states of lanthanide emitters are often quenched by the interior lattice defects and deleterious interactions among different lanthanides, resulting in weak ultraviolet emission. Here, we describe a novel excitation energy lock-in approach to boost ultraviolet upconversion emission in a new class of multilayer core-shell nanoparticles with a gadolinium-rich core domain. Remarkably, we observe more than 70-fold enhancements in Gd3+ emission from the designed nanoparticles compared with the conventional nanoparticles. Our mechanistic investigation reveals that the combination of energy migration over the core domain and optically inert NaYF4 interlayer can effectively confine the excitation energy and thus lead to intense multiphoton ultraviolet emission in upconversion nanostructures. We further achieve a 35.6% increase in photocatalytic reactivity and 26.5% in reactive oxygen species production yield in ZnO-coated upconversion nanocomposites under 808-nm excitation. This study provides a new insight to energy transfer mechanism in lanthanide-doped nanoparticles and offers an exciting avenue for exploring novel near-infrared photocatalysts.

Microsphere Photonic Superlens for a Highly Emissive Flexible Upconversion-Nanoparticle-Embedded Film

Increasing upconversion luminescence (UCL) to overcome the intrinsically low conversion efficiency of upconversion nanoparticles (UCNPs) poses a fundamental challenge. Photonic nanostructures are the efficient approaches for UCL enhancement by tailoring the local electromagnetic fields. Unfortunately, such nanostructures are sensitive to environmental conditions, and the regulation strength is varied in flexible applications. Here, we report giant UCL enhancement from a flexible UCNP-embedded film coupled with a microsphere photonic superlens (MPS), by which the enhancement ratio of UCL is over 104-fold under 808 nm excitation down to 0.72 mW. The enhancement pathways of MPS-enhanced UCL are attributed to Mie-resonant nanofocusing for high excitation-photon density, optical whispering-gallery modes (WGMs) for fast radiative decay, and the directional antenna effect for far-field emission confinement. The contribution of optical resonance in the MPS to suppressing the phonon-induced nonradiative transition and thermal quenching is experimentally validated. The UCL quantum yield is therefore improved by 3-fold to 4.20% under 120 mW/cm2 near-infrared excitation, consistent with the enhancement ratio via the Purcell effect of WGMs. Furthermore, the MPS demonstrates the robust optical regulation capability toward flexible applications, opening up new opportunities for facilitating multiphoton upconversion in wearable optoelectrical devices for nanoimaging, biosensing, and energy conversion in the future.

Nanosecond kinetics of multiphoton upconversion in an optically trapped single microcrystal

Here, we built a setup that can optically trap single microcrystals (MCs) in solution, and determine the time-resolved multiband upconversion luminescence at a nanosecond timescale.

Dye Sensitization for Ultraviolet Upconversion Enhancement.

Upconversion nanocrystals that converted near-infrared radiation into emission in the ultraviolet spectral region offer many exciting opportunities for drug release, photocatalysis, photodynamic therapy, and solid-state lasing. However, a key challenge is the development of lanthanide-doped nanocrystals with efficient ultraviolet emission, due to low conversion efficiency. Here, we develop a dye-sensitized, heterogeneous core–multishelled lanthanide nanoparticle for ultraviolet upconversion enhancement. We systematically study the main influencing factors on ultraviolet upconversion emission, including dye concentration, excitation wavelength, and dye-sensitizer distance. Interestingly, our experimental results demonstrate a largely promoted multiphoton upconversion. The underlying mechanism and detailed energy transfer pathway are illustrated. These findings offer insights into future developments of highly ultraviolet-emissive nanohybrids and provide more opportunities for applications in photo-catalysis, biomedicine, and environmental science.

Multiphoton upconversion and non-resonant optical nonlinearity in perovskite quantum dot doped glasses.

By incorporating the CsPbBr3 quantum dots (QDs) into a glass host, we report for the first time, to our knowledge, the measurement of non-resonant optical nonlinearity and multiphoton upconversion (UC) processes for this QD-in-glass composite. We observe up to four-photon stable UC photoluminescence under excitation by infrared femtosecond pulses, low optical limiting thresholds, and high nonlinear optical absorption coefficients close to those of colloid processed metal halide perovskite (MHP) QDs. Combined with high robustness against air and moisture, the monolithic inorganic glass with incorporated MHP QDs could be a better platform for exploiting strong light-matter interaction for MHPs.

Multiphoton Upconversion Materials for Photocatalysis and Environmental Remediation.

Solar-driven photocatalysis holds great potential for energy conversion, environmental remediation, and sustainable chemistry. However, practical applications of conventional photocatalytic systems have been constrained by their insufficient ability to harvest solar radiation in the infrared spectrum. Lanthanide-doped upconversion materials possess high photostability, tunable absorption, and the ability to convert low-energy infrared radiation into high-energy emission, making them attractive for infrared-driven photocatalysis. This review highlights essential principles for rational design of efficient photocatalysts. Particular emphasis is placed on current state-of-the-arts that offer enhanced upconversion luminescence efficiency. We also summarize recent advances in lanthanide-doped upconversion materials for photocatalysis. We conclude with new challenges and prospects for future developments of infrared-driven photocatalysts.

(Invited) Theranostics with Lanthanide Doped Nanoparticles

In recent years, a significant amount of research has focused on nanoparticle-based “theranostic” agents for the treatment of a wide array of diseases, including cancer. This new paradigm in personalized medicine intends to exploit nanoplatforms that carry both therapeutic and diagnostic (theranostic) modalities. Compared with delivering drugs or imaging agents separately, theranostic agents can simultaneously deliver them to specific sites, enabling detection and treatment of disease in a single procedure. Many theranostic nanoplatforms are triggered by light, however, the vast majority of these are limited in that the ultraviolet or visible excitation light used has minimal applicability in biological applications. Lanthanide doped nanoparticles, on the other can be excited with biologically friendly near-infrared light (in the biological windows) and can emit in the ultraviolet, visible or near-infrared regions through a multiphoton upconversion process while simultaneously emitting in the near-infrared region through a Stokes or downshifted process. Hence, the upconversion luminescence can be used to trigger the therapeutic application (drug delivery, photodynamic therapy, etc.) while the near-infrared luminescence can be used for the diagnostic modality (bioimaging, nanothermometry, etc).In this presentation, we will introduce lanthanide doped nanoparticles and demonstrate their usefulness in theranostics. In particular, we will show complex nanoparticle architectures can endow further functionality to these nanoparticles including the ability to decouple the theranostic processes that are conventionally delivered simultaneously.

Multiphoton Upconversion Enhanced by Deep Subwavelength Near-Field Confinement.

Efficient generation of anti-Stokes emission within nanometric volumes enables the design of ultracompact, miniaturized photonic devices for a host of applications. Many subwavelength crystals, such as metal nanoparticles and two-dimensional layered semiconductors, have been coupled with plasmonic nanostructures for augmented anti-Stokes luminescence through multiple-harmonic generation. However, their upconversion process remains inefficient due to their intrinsic low absorption coefficients. Here, we demonstrate on-chip, site-specific integration of lanthanide-activated nanocrystals within gold nanotrenches of sub-25 nm gaps via bottom-up self-assembly. Coupling of upconversion nanoparticles to subwavelength gap-plasmon modes boosts 3.7-fold spontaneous emission rates and enhances upconversion by a factor of 100 000. Numerical investigations reveal that the gap-mode nanocavity confines incident excitation radiation into nanometric photonic hotspots with extremely high field intensity, accelerating multiphoton upconversion processes. The ability to design lateral gap-plasmon modes for enhanced frequency conversion may hold the potential to develop on-chip, background-free molecular sensors and low-threshold upconversion lasers.

Enhancing multiphoton upconversion emissions through confined energy migration in lanthanide-doped Cs2NaYF6 nanoplatelets.

Lanthanide (Ln3+)-doped upconversion (UC) nanocrystals have drawn tremendous attention because of their intriguing optical properties. Currently, it is highly desired but remains challenging to achieve efficient multiphoton UC emissions. Herein, we report the controlled synthesis of a new class of UC nanocrystals based on Cs2NaYF6:Yb/Tm nanoplatelets (NPs), which can effectively convert the 980 nm light to five-photon and four-photon UC emissions of Tm3+ without the fabrication of a complicated core/multishell structure required in traditional nanocrystals. Particularly, the as-prepared Cs2NaYF6:Yb/Tm NPs exhibit a maximal UV-to-NIR emission intensity ratio of 1.2, which is the highest among Tm3+-doped core-only UC nanocrystals. We reveal that the enhanced multiphoton UC emissions may benefit from the confined energy migration of Ln3+ dopants in the unique two-dimensional-like structure of Cs2NaYF6 NPs. As such, intense red and green UC emissions of Eu3+ and Tb3+ can further be generated via the cascade sensitization of Tm3+ and Gd3+ in Cs2NaYF6:Yb/Tm/Gd/Eu and Cs2NaYF6:Yb/Tm/Gd/Tb NPs, respectively. These results validate the superiority of Cs2NaYF6 for the future design of efficient UC nanocrystals towards versatile applications.