Lanthanide-based Upconversion Research Articles

Upconversion Luminescence in a Photostable Ion-Paired Yb-Eu Heteronuclear Complex.

Lanthanide-based upconversion molecular complexes have potential application in diverse fields and attracted considerable research interest in recent years. However, the similar coordination reactivity of lanthanide ions has constrained the designability of target molecule with well-defined structure, and many attempts obtained statistical mixtures. Herein, an ion-paired Yb-Eu heteronuclear complex [Eu(TpPy)2][Yb(ND)4] (TpPy = tris[3-(2-pyridyl)pyrazolyl]hydroborate, ND = 3-cyano-2-methyl-1,5-naphthyridin-4-olate) was designed and synthesized. Thanks to the radius difference between Eu3+ (1.07 Å) and Yb3+ (0.98 Å) ions, the hexadentate TpPy ligand was selected to coordinate with Eu3+ and the Yb3+ with a smaller radius was chelated by bidentate ND ligand. As a result, the sites of Eu3+ and Yb3+ in the complex can be clarified by high-resolution mass spectrometry and single-crystal structure analysis. Upon the excitation of Yb3+ at 980 nm, the upconversion emission of Eu3+ was realized through a cooperative sensitization process. Furthermore, [Eu(TpPy)2][Yb(ND)4] demonstrated excellent photostability during continuous high-power density 980 nm laser irradiation, with a LT95 (the time to 95% of the initial emission intensity) of 420 minutes. This work provides the first example of a pure ion-paired Yb-Eu heteronuclear complex upconversion system and may bring insights into rational design of lanthanide-based upconversion molecular complexes.

Emerging trends in lanthanide-based upconversion and downconversion material for PSCs & DSSCs

Emerging trends in lanthanide-based upconversion and downconversion material for PSCs & DSSCs

Ultrastrong up-conversion luminescence in inert-active-inert sandwich structure with critical inert-core size

Lanthanide-based up-conversion materials exhibit abundant emission colors under infrared excitation; however, enhancing their up-conversion luminescence efficiency remains a hot topic and a challenge. Here, we show ultra-strong up-conversion luminescence in an inert-active-inert sandwich structure with critical core sizes. It is observed that the emission intensity of the sandwich structure (NaYF4@NaYbF4:0.5 %Tm@ NaYF4) is equal to ∼ 129 times of that in the NaYF4@NaYbF4:0.5 %Tm core/shell nanoparticles and 64 times of that in the NaYbF4:0.5 %Tm@Y core/shell nanoparticles. Moreover, it is more than a tenfold enhancement compared to the well-known classic core–shell structures (NaYF4:20 %Yb, 0.5 %Tm@NaYF4). By restricting the activator to 2D planes, their interactions with vacancies that are randomly distributed in 3D space are minimized. As a result, the energy transfer rate of Yb3+ defects is suppressed in this sandwich structure, while further effectively maintaining or enhancing the energy transfer from Yb3+ to the activator. Worth mentioning is that the strongest up-conversion luminescence is observed in the inert-active-inert sandwich structure with a critical inert core size of approximately 85 nm, which is in good agreement with the inflexion point of the calculated the effective excitation volume per unit cross-section.

Clustering triggered emissive liquid crystalline template for dual mode upconverted and downconverted circularly polarized luminescence.

Liquid crystalline materials have attracted significant attention in chiroptical research due to their ability to form long range ordered helical superstructures. Research focus has been on exploiting the unique properties of liquid crystalline materials to demonstrate highly dissymmetric circularly polarised luminescent (CPL) systems. In this study, we present a thermally driven, facile approach to fabricate CPL-active materials utilizing cholesteryl benzoate as the active substrate. Cholesteryl benzoate, a well-known thermotropic liquid crystal, has been found to manifest intriguing optical characteristics upon subjecting to repeated heating-cooling cycles. Despite the absence of conventional fluorescent moieties, the material exhibited luminescence through aggregation induced clustering triggered emission mechanism. Systematic investigations revealed excitation-dependent CPL for solid cholesteryl benzoate films when subjected to multiple thermal cycles. The excited state chiroptical investigation performed after multiple thermal cycles showed a luminescence anisotropy (glum) of 8 × 10-2, which is a high value for simple organic molecules. Moreover, upon co-assembly with lanthanide-based upconversion nanophosphors (UCNPs), the hybrid system demonstrated upconverted circularly polarised luminescence (UC-CPL). Benefiting from the ability to endow upconversion nanoparticles of various sizes, fabrication of UCNP-ChB hybrid nanocomposites exhibiting multicoloured upconversion CPL was demonstrated. These findings highlight the potential of liquid crystalline materials for diverse applications, including 3D optical displays and anticounterfeiting technologies.

Control of Luminescence and Interfacial Properties as Perspective for Upconversion Nanoparticles.

Near-infrared (NIR) light is highly suitable for studying biological systems due to its minimal scattering and lack of background fluorescence excitation, resulting in high signal-to-noise ratios. By combining NIR light with lanthanide-based upconversion nanoparticles (UCNPs), upconversion is used to generate UV or visible light within tissue. This remarkable property has gained significant research interest over the past two decades. Synthesis methods are developed to produce particles of various sizes, shapes, and complex core-shell architectures and new strategies are explored to optimize particle properties for specific bioapplications. The diverse photophysics of lanthanide ions offers extensive possibilities to tailor spectral characteristics by incorporating different ions and manipulating their arrangement within the nanocrystal. However, several challenges remain before UCNPs can be widely applied. Understanding the behavior of particle surfaces when exposed to complex biological environments is crucial. In applications where deep tissue penetration is required, such as photodynamic therapy and optogenetics, UCNPs show great potential as nanolamps. These nanoparticles can combine diagnostics and therapeutics in a minimally invasive, efficient manner, making them ideal upconversion probes. This article provides an overview of recent UCNP design trends, highlights past research achievements, and outlines potential future directions to bring upconversion research to the next level.

Boosting Dye-Sensitized Luminescence by Enhanced Short-Range Triplet Energy Transfer.

Dye-sensitization can enhance lanthanide-based upconversion luminescence, but is hindered by interfacial energy transfer from organic dye to lanthanide ion Yb3+ . To overcome these limitations, modifying coordination sites on dye conjugated structures and minimizing the distance between fluorescence cores and Yb3+ in upconversion nanoparticles (UCNPs) are proposed. The specially designed near-infrared (NIR) dye, disulfo-indocyanine green (disulfo-ICG), acts as the antenna molecule and exhibits a 2413-fold increase in luminescence under 808nm excitation compared to UCNPs alone using 980nm irradiation. The significant improvement is attributed to the high energy transfer efficiency of 72.1% from disulfo-ICG to Yb3+ in UCNPs, with majority of energy originating from triplet state (T1 ) of disulfo-ICG. Shortening the distance between the dye and lanthanide ions increases the probability of energy transfer and strengthens the heavy atom effect, leading to enhanced T1 generation and improved dye-triplet sensitization upconversion. Importantly, this approach also applies to 730nm excitation Cy7-SO3 sensitization system, overcoming the spectral mismatch between Cy7 and Yb3+ and achieving a 52-fold enhancement in luminescence. Furthermore, the enhancement of upconversion at single particle level through dye-sensitization is demonstrated. This strategy expands the range of NIR dyes for sensitization and opens new avenues for highly efficient dye-sensitized upconversion systems.

Up-conversion phosphor Na2MoO4:Er3+/Yb3+ for the optical temperature sensing and anti-counterfeiting

Lanthanide-based upconversion (UC) materials exhibit remarkable temperature-sensing properties as excited by near-infrared light. This article aims to investigate the UC emission and its temperature-sensing behavior of Na2MoO4:Er3+/Yb3+. The molybdate powder Na2MoO4:Er3+, Yb3+ shows bright green UC emission under a 980 nm laser. By monitoring the temperature-dependent green emission, the optical thermometric properties of Na2MoO4:xEr3+/0.01 Yb3+ are investigated. 1.38% K−1 is the maximum absolute sensitivity (SA) and the relative sensitivity (SR) is 1.21% K−1 with a 0.09–0.22 K temperature resolution (ΔT) at 0.001Er3+. The material was successfully combined with acrylic to prepare invisible anti-counterfeit patterns. These significant findings provide a theoretical foundation for temperature-sensing capabilities and potential applications in anti-counterfeiting measures.

Plasmon Modulated Upconversion Biosensors

Over the past two decades, lanthanide-based upconversion nanoparticles (UCNPs) have been fascinating scientists due to their ability to offer unprecedented prospects to upconvert tissue-penetrating near-infrared light into color-tailorable optical illumination inside biological matter. In particular, luminescent behavior UCNPs have been widely utilized for background-free biorecognition and biosensing. Currently, a paramount challenge exists on how to maximize NIR light harvesting and upconversion efficiencies for achieving faster response and better sensitivity without damaging the biological tissue upon laser assisted photoactivation. In this review, we offer the reader an overview of the recent updates about exciting achievements and challenges in the development of plasmon-modulated upconversion nanoformulations for biosensing application.

Magnetic modification of lanthanide-based upconversion nanocrystals for fingerprint information recognition

The development of new magnetic fluorescent materials is of great significance for identification and criminal investigation. Since the photosensitive elements used in conventional cameras have exhibited the highest quantum efficiency in the range of 500–700 nm, lanthanide-based upconversion nanoparticles (UCNPs) with main emission peaks at 507–533 nm, 533–568 nm and 637–683 nm are suitable for constructing magnetic fluorescent materials. In this work, we demonstrate a type of magnetic upconversion nanoparticle (MUCNP) of NaGdF<sub>4</sub>:Yb,Er-Fe<sub>3</sub>O<sub>4</sub> by a ligand-linked method. After optimizing the reaction parameters, the composite particles possess remarkable magnetic properties and upconversion fluorescence intensity and achieve high contrast for latent fingerprint recognition on various substrates. The combination of upconversion luminescence and magnetism contributes to good fingerprint recognition sensitivity and universality.

Upconversion Luminescence through Cooperative and Energy-Transfer Mechanisms in Yb3+ -Metal-Organic Frameworks.

Lanthanide-doped metal-organic frameworks (Ln-MOFs) have versatile luminescence properties, however it is challenging to achieve lanthanide-based upconversion luminescence in these materials. Here, 1,3,5-benzenetricarboxylic acid (BTC) and trivalent Yb3+ ions were used to generate crystalline Yb-BTC MOF 1D-microrods with upconversion luminescence under near infrared excitation via cooperative luminescence. Subsequently, the Yb-BTC MOFs were doped with a variety of different lanthanides to evaluate the potential for Yb3+ -based upconversion and energy transfer. Yb-BTC MOFs doped with Er3+ , Ho3+ , Tb3+ , and Eu3+ ions exhibit both the cooperative luminescence from Yb3+ and the characteristic emission bands of these ions under 980 nm irradiation. In contrast, only the 497 nm upconversion emission band from Yb3+ is observed in the MOFs doped with Tm3+ , Pr3+ , Sm3+ , and Dy3+ . The effects of different dopants on the efficiency of cooperative luminescence were established and will provide guidance for the exploitation of Ln-MOFs exhibiting upconversion.

Cubic upconversion nanoparticles used as the theranostic system for the treatment and diagnosis of angiogenesis-related diseases

Biocompatible nanostructures offer new pathways to overcome the obstacles in conventional anti-angiogenic therapy such as drug accumulation and therapeutic efficiency. However, current technology is limited by the bioavailability of therapeutics and the obstruction of imaging. Theranostic nanoparticles have been developed to bridge the gap between imaging and therapeutic delivery. In this paper, a theranostic system made of cubic lanthanide-based upconversion nanoparticles (UCNPs) has been developed. The average length of the cubic UCNPs is estimated at 53 ± 13 nm. The fluorescence intensity of the emission peaks of UNCPs in the visible range is dependent on the power of the excitation at a region of near-infrared (NIR), λex = 980 nm. In addition, cell imaging has demonstrated that the UNCPs conjugated with anti-VEGF antibodies show significant anti-angiogenic effects which are even stronger than their anti-VEGF counterpart. With the capabilities of both anti-angiogenic effects and cell imaging, the UCNPs-antiVEGF is a promising theranostic model at the nanoscale for the treatment and diagnosis of angiogenesis-related diseases .

A Facile Approach for the Ligand Free Synthesis of Biocompatible Upconversion Nanophosphors.

Upconversion nanophosphors, particles that can absorb low energy radiation and emit high energy light through multi-photon absorption processes, have gained augmented attention in recent years. Due to their admirable optical and chemical properties, these nanoparticles are finding wide range of applications in the field of bioimaging, light emitting devices and security printing. However, for any practical application, it is extremely important that a facile synthetic route is developed that can lead to the generation of nanophosphors exhibiting efficient upconversion luminescence under diverse experimental conditions. Herein, we report a new ligand-free approach for the synthesis of lanthanide-based upconversion nanoparticles by adopting a simple solid-state synthetic route. The reaction conditions such as temperature and time were optimized to obtain nanophosphors exhibiting enhanced upconversion luminescence. The synthesized nanoparticles, due to its ligand-free nature, could be well dispersed in both aqueous and organic media. The nanophosphors retained the upconversion luminescence under varying time, pH and temperature, indicating that the absence of ligand had least effect on their stability. The nanophosphors were found to exhibit good cell viability even under high concentrations, unveiling their potential as bioimaging agents in the biomedical research.

Expanding the toolbox of photon upconversion for emerging frontier applications.

Photon upconversion in lanthanide-based materials has recently shown compelling advantages in a wide range of fields due to their exceptional anti-Stokes luminescence performances and physicochemical properties. In particular, the latest breakthroughs in the optical manipulation of photon upconversion, such as the precise tuning of switchable emission profiles and lifetimes, open up new opportunities for diverse frontier applications from biological imaging to therapy, nanophotonics and three-dimensional displays. A summary and discussion on the recent progress can provide new insights into the fundamental understanding of luminescence mechanisms and also help to inspire new upconversion concepts and promote their frontier applications. Herein, we present a review on the state-of-the-art progress of lanthanide-based upconversion materials, focusing on the newly emerging approaches to the smart control of upconversion in aspects of light intensity, colors, and lifetimes, as well as new concepts. The emerging scientific and technological discoveries based on the well-designed upconversion materials are highlighted and discussed, along with the challenges and future perspectives. This review will contribute to the understanding of the fundamental research of photon upconversion and further promote the development of new classes of efficient upconversion materials towards diversities of frontier applications in the future.

Harvesting Sub-bandgap Photons via Upconversion for Perovskite Solar Cells.

Lanthanide-based upconversion (UC) allows harvesting sub-bandgap near-infrared photons in photovoltaics. In this work, we investigate UC in perovskite solar cells by implementing UC single crystal BaF2:Yb3+, Er3+ at the rear of the solar cell. Upon illumination with high-intensity sub-bandgap photons at 980 nm, the BaF2:Yb3+, Er3+ crystal emits upconverted photons in the spectral range between 520 and 700 nm. When tested under terrestrial sunlight representing one sun above the perovskite's bandgap and sub-bandgap illumination at 980 nm, upconverted photons contribute a 0.38 mA/cm2 enhancement in the short-circuit current density at lower intensity. The current enhancement scales non-linearly with the incident intensity of sub-bandgap illumination, and at higher intensity, 2.09 mA/cm2 enhancement in current was observed. Hence, our study shows that using a fluoride single crystal like BaF2:Yb3+, Er3+ for UC is a suitable method to extend the response of perovskite solar cells to near-infrared illumination at 980 nm with a subsequent enhancement in current for very high incident intensity.

Photon Upconversion for Photovoltaics and Photocatalysis: ACriticalReview.

Opportunities for enhancing solar energy harvesting using photon upconversion are reviewed. The increasing prominence of bifacial solar cells is an enabling factor for the implementation of upconversion, however, when the realistic constraints of current best-performing silicon devices are considered, many challenges remain before silicon photovoltaics operating under nonconcentrated sunlight can be enhanced via lanthanide-based upconversion. A photophysical model reveals that >1-2 orders of magnitude increase in the intermediate state lifetime, energy transfer rate, or generation rate would be needed before such solar upconversion could start to become efficient. Methods to increase the generation rate such as the use of cosensitizers to expand the absorption range and the use of plasmonics or photonic structures are reviewed. The opportunities and challenges for these approaches (or combinations thereof) to achieve efficient solar upconversion are discussed. The opportunity for enhancing the performance of technologies such as luminescent solar concentrators by combining upconversion together with micro-optics is also reviewed. Triplet-triplet annihilation-based upconversion is progressing steadily toward being relevant to lower-bandgap solar cells. Looking toward photocatalysis, photophysical modeling indicates that current blue-to-ultraviolet lanthanide upconversion systems are very inefficient. However, hope remains in this direction for organic upconversion enhancing the performance of visible-light-active photocatalysts.

Transparent and flexible resins functionalized by lanthanide-based upconversion nanocrystals.

Functional resins with optical adjustment capability own great potential in multiple application scenarios. To this end, we functionalize resins with upconversion nanocrystals (UCNCs), namely an UCNC-Au composite structure, to endow them with the unique ability of converting near-infrared (NIR) radiation into visible-light emission. Such UCNC-functionalized resins with high transparency and flexibility are expected to accelerate the development in the comprehensive utilization of NIR during practical applications.

Mono- to few-layer non-van der Waals 2D lanthanide-doped NaYF4 nanosheets with upconversion luminescence

NaYF4 is an efficient host material for lanthanide-based upconversion luminescence and has attracted immense interest for potential applications in photovoltaics, lasers and bioimaging. However, being a non-van der Waals (non-vdW) material, there have been thus far no reports on exfoliation of bulk NaYF4 to nanosheets and their upconversion luminescence properties. Here, we demonstrate for the first time the fabrication of lanthanide-containing NaYF4 2D nanosheets using a soft liquid-phase exfoliation method and report on their optical, electronic and chemical characteristics. The nanosheets exfoliated from NaYF4:Yb,Er microcrystals consisting mainly of β-NaYF4 become enriched in α-NaYF4 post exfoliation and have a large micron-sized planar area with a preferential (100) surface orientation. X-ray absorption spectroscopy confirms that both Yb and Er doping ions are retained in the exfoliated nanosheets. Through centrifugation, NaYF4 2D nanosheets are successfully obtained with thicknesses ranging from a monolayer to tens of layers. Optical analysis of individual nanosheets shows that they exhibit both optical down-conversion and upconversion properties, albeit with reduced emission intensities compared with the parent microparticles. Further exploration of their electronic structure by density functional theory (DFT) calculations and photoelectron spectroscopy reveals the formation of surface F atom defects and a shrinkage of the electronic bandgap in ultrathin nanosheets. Our findings will trigger further interest in non-vdW 2D upconversion nanomaterials.

Microscale Self-Assembly of Upconversion Nanoparticles Driven by Block Copolymer.

Lanthanide-based upconversion nanoparticles can convert low-energy excitation to high-energy emission. The self-assembled upconversion nanoparticles with unique structures have considerable promise in sensors and optical devices due to intriguing properties. However, the assembly of isotropic nanocrystals into anisotropic structures is a fundamental challenge caused by the difficulty in controlling interparticle interactions. Herein, we report a novel approach for the preparation of the chain-like assemblies of upconversion nanoparticles at different scales from nano-scale to micro-scale. The dimension of chain-like assembly can be fine-tuned using various incubation times. Our study observed Y-junction aggregate morphology due to the flexible nature of amphiphilic block copolymer. Furthermore, the prepared nanoparticle assemblies of upconversion nanoparticles with lengths up to several micrometers can serve as novel luminescent nanostructure and offer great opportunities in the fields of optical applications.

Light-Emitting Diode Excitation for Upconversion Microscopy: A Quantitative Assessment

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 inert shell protection become clearly identified under LED excitation at 1.18 W cm-2, as confirmed by correlated electron microscopy images. Hydrophilic UCNPs are obtained by polysaccharide coating via a facile ligand exchange protocol to demonstrate imaging of cellular uptake using LED excitation. These results suggest a viable approach to bypassing the limitations associated with high-power lasers when applying UCNPs and upconversion microscopy to life science research.

Stretchable and upconversion-luminescent polymeric optical sensor for wearable multifunctional sensing.

Stretchable sensors with multiple sensory functions are in high demand for healthcare monitoring and artificial intelligence. Despite recent advances in wearable electronic sensors, it remains a significant challenge to achieve simultaneous sensing of both thermal and mechanical stimuli with a single sensor while integrating high stretchability. Herein, a stretchable and multifunctional optical sensor (SMOS) with simultaneous readout of temperature and strain is developed for wearable physiological monitoring of the human body. The SMOS primarily consists of a stretchable optical sensing fiber made from polymer nanocomposites containing lanthanide-based upconversion nanoparticles (UCNPs). Temperature measurements are achieved by ratiometric intensity measurements of the dual-emission UCNPs upon near-infrared excitation. By virtue of the ratiometric detection, the temperature readout of the SMOS is independent of strain deformations, enabling stable and continuous measurements of skin temperature during body motions. Furthermore, deformation of the SMOS by stretching leads to detectable and reversible changes in its light transmission, allowing tensile strains to be simultaneously measured. As a proof of concept, we demonstrate the capabilities of the SMOS in real time and simultaneous detection of both skin temperature and motion activities of the human body.