Lanthanide-doped Nanomaterials Research Articles

Dual-mode excitable Vis/NIR-II luminescence of lanthanide-doped core@multishell nanostructures for anti-counterfeiting and imaging of latent fingerprints

The development of luminescent materials that can simultaneously realize multiple emissions can help improve the reliability of anti-counterfeiting and the security of encrypted information. Lanthanide-doped nanomaterials are very suitable for advanced anti-counterfeiting applications because of their abundant 4 f energy levels and near-infrared (NIR) laser excitability. Herein, we design lanthanide-doped core@multishell nanoparticles NaYF4:Yb,Er/Ho/Tm@NaYF4@NaYF4:Nd@NaYF4, which can realize upconversion luminescence of Er/Ho/Tm under 980 nm excitation, as well as non-overlapping NIR-II luminescence under 980 nm or 808 nm excitation. By precisely controlling the distribution of lanthanide ions in the core-shell layer, the luminescence interference of nanomaterials under different wavelength excitation can be avoided. Experiments show that multi-color security and information encryption under NIR laser excitation can be achieved using aqueous inks containing the designed multilayered core-shell nanostructures, which are covert and difficult to forge. And the multilayer core-shell nanopowder can be used for efficient identification of latent fingerprints on complex surfaces.

Er3+/Tm3+ co-activated core@shell nanoarchitectures: tunable upconversion luminescence and high-security anti-counterfeiting

Currently, developing advanced optoelectronic materials is of great importance to solving serious problem of fake and shoddy products. Lanthanide-doped nanomaterials are particularly suitable for addressing this issue, but limited by the realization of multiple upconverison (UC) emissions upon a single-wavelength laser excitation. Herein, it is proven that the co-dopant of blue/near-infrared (NIR)-emitting activators (Tm3+) and green/red-emitting centers (Er3+) in a particular designed core–shell nanoarchitecture allows the achievement of multiple luminescence over wide spectral region for optical security. In our study, cubic-phased NaYbF4:Tm/Er@CaF2 nanocrystals have been successfully synthesized through a layer-by-layer coprecipitation strategy, which presents visible multicolor UC luminescence and invisible NIR UC emission upon 980 nm laser excitation by just regulating the laser power and temperature. Significantly, the unique luminescent characteristics enables the designed UC nanoparticles a promising candidate for advanced anti-counterfeiting. This works offers a reference to develop advanced optoelectronic materials for practical application in optical security.

Responsive Regulation of Energy Transfer in Lanthanide-Doped Nanomaterials Dispersed in Chiral Nematic Structure.

The responsive control of energy transfer (ET) plays a key role in the broad applications of lanthanide-doped nanomaterials. Photonic crystals (PCs) are excellent materials for ET regulation. Among the numerous materials that can be used to fabricate PCs, chiral nematic liquid crystals are highly attractive due to their good photoelectric responsiveness and biocompatibility. Here, the mechanisms of ET and the photonic effect of chiral nematic structures on ET are introduced; the regulation methods of chiral nematic structures and the resulting changes in ET of lanthanide-doped nanomaterials are highlighted; and the challenges and promising opportunities for ET in chiral nematic structures are discussed.

Metal plasmon-enhanced lanthanide fluorescent nanoparticles for monitoring aqueous copper ions

Lanthanide-doped nanomaterials displaying intense, explicit, and long-lasting photoluminescence (PL) have gained much attention in sensing and imaging applications. In this work, europium complex Eu(dibenzoylmethane)3(1,10-phenanthroline) was integrated into core-shell magnetoplasmonic nanoparticles (Ag@Fe3O4 MagPlas NPs), forming a photoluminescent MagPlas nanostructure with uniform morphology, sharp PL emission profile, and distinct magnetic response. The Eu-doped MagPlas NPs (Eu-MagPs) with Ag-core exhibited an enhancement of PL intensity and lifetime compared to the non-plasmonic counterpart, owing to the metal plasmon-induced fluorescence enhancement. Moreover, the quenching phenomenon of the Eu-MagP probe was utilized as a platform for active quantification of metal ion concentration, exclusively Cu2+, in aqueous samples. The luminescence intensity from the Eu-doped MagPlas NP was proportionally quenched by Cu2+ in the working range of 0–2 ppm with negligible influences of other common cations and anions. Static quenching was investigated as the main mechanism for selective detection, in which the presence of quenchers did not affect the luminescent lifetime of the hybrid nanostructure. Moreover, Eu-MagPs were integrated into polyacrylamide hydrogels with enhanced customizability toward the varied amounts of Cu2+. This fluorescent MagPlas structure, therefore, can be utilized as versatile, waste-free, fully recoverable testing assays or chemical sensors for on-site environmental analysis, and water quality control.

Lanthanide-doped heterostructured nanocomposites toward advanced optical anti-counterfeiting and information storage

The continuously growing importance of information storage, transmission, and authentication impose many new demands and challenges for modern nano-photonic materials and information storage technologies, both in security and storage capacity. Recently, luminescent lanthanide-doped nanomaterials have drawn much attention in this field because of their photostability, multimodal/multicolor/narrowband emissions, and long luminescence lifetime. Here, we report a multimodal nanocomposite composed of lanthanide-doped upconverting nanoparticle and EuSe semiconductor, which was constructed by utilizing a cation exchange strategy. The nanocomposite can emit blue and white light under 365 and 394 nm excitation, respectively. Meanwhile, the nanocomposites show different colors under 980 nm laser excitation when the content of Tb3+ ions is changed in the upconversion nanoparticles. Moreover, the time-gating technology is used to filter the upconversion emission of a long lifetime from Tb3+ or Eu3+, and the possibilities for modulating the emission color of the nanocomposites are further expanded. Based on the advantage of multiple tunable luminescence, the nanocomposites are designed as optical modules to load optical information. This work enables multi-dimensional storage of information and provides new insights into the design and fabrication of next-generation storage materials.

Luminescent Lifetime Regulation of Lanthanide-Doped Nanoparticles for Biosensing.

Lanthanide-doped nanoparticles possess numerous advantages including tunable luminescence emission, narrow peak width and excellent optical and thermal stability, especially concerning the long lifetime from microseconds to milliseconds. Differing from other shorter-lifetime fluorescent nanomaterials, the long lifetime of lanthanide-doped nanomaterials is independent with background fluorescence interference and biological tissue depth. This review presents the recent advances in approaches to regulating the lifetime and applications of bioimaging and biodetection. We begin with the introduction of the strategies for regulating the lifetime by modulating the core–shell structure, adjusting the concentration of sensitizer and emitter, changing energy transfer channel, establishing a fluorescence resonance energy transfer pathway and changing temperature. We then summarize the applications of these nanoparticles in biosensing, including ion and molecule detecting, DNA and protease detection, cell labeling, organ imaging and thermal and pH sensing. Finally, the prospects and challenges of the lanthanide lifetime regulation for fundamental research and practical applications are also discussed.

Dual-mode luminescent multilayer core-shell UCNPs@SiO2@TEuTbB nanospheres for high-level anti-counterfeiting and recognition of latent fingerprints

Currently, illegal counterfeiting activities are increasing with the continuous developments of society and the fabrication of high security anti-counterfeiting techniques is becoming essential. The lanthanide-doped nanomaterials have great potential in anti-counterfeiting for their high luminescence intensity, narrow half-peak width and high stability. Herein, the dual-mode luminescent UCNPs@SiO2@TEuTbB nanomaterials have been successfully fabricated for anti-counterfeiting. Morphology, structure and luminesce properties of the synthetic samples have been investigated via TEM, XRD, FT-IR, XPS and fluorescence spectroscopy. The results present that the size of the synthetic materials is about 100 nm. The luminesce properties clearly show that the UCNPs@SiO2@TEuTbB nanomaterials can emit strong UC red color under the NIR light. Meanwhile, these materials can emit several DC luminescence colors by adjusting Eu3+ ions concentration under UV lamp. Furthermore, the lanthanide-doped nanomaterials are widely used in recognition of LFPs providing valuable evidence in forensic filed. As a result, the images of LFPs developed by the as prepared materials on various surfaces under UV lamp can be well visualized. The three levels details of fingerprints are clearly visible with high sensitivity, selectivity and contrast. Thus, these results confirm that the synthetized UCNPs@SiO2@TEuTbB nanospheres can provide a foundation for high-level anti-counterfeiting and the detection of fingerprints.

Colour modulation and enhancement of upconversion emissions in K2NaScF6:Yb/Ln (Ln = Er, Ho, Tm) nanocrystals

Effective colour modulation of upconversion emissions in lanthanide-doped nanomaterials becomes even more important for fundamental and applied research. Herein, on the one hand, by raising the content of doped Yb3+ from 10 mol% to 50 mol%, a significant increase of the red/green emission ratio from 4.0 to 68.2 is observed in K2NaScF6:Yb/Er nanocrystals. This yellow to red colour change is attributed to the increased cross relaxation between Er3+ and Yb3+ caused by the increased Yb3+ amount, 4S3/2 (Er3+) + 2F7/2 (Yb3+) → 4I13/2 (Er3+) + 2F5/2 (Yb3+). On the other hand, the upconversion green and red emission of K2NaScF6:Yb/Er (20/2 mol%) nanocrystals are intensified 10.6 and 8.8 folds, respectively, after an active shell (K2NaScF6:Yb) is epitaxially grown, which are more effective than the 7.4- and 6.4-fold enhancement from an inert shell (K2NaScF6) growth. Moreover, the shell thickness from 2.85 to 9.5 nm through controlling the molar ratio of shell-precursor to core from 1:2 to 3:1 can be easily realized. This study will provide more opportunities for the application of K2NaScF6:Yb/Ln nanoparticles in varied fields such as theranostics, photovoltaics, and photocatalysis.

Time-resolved Imaging Using Lanthanide-doped Nanomaterials

Time-resolved Imaging Using Lanthanide-doped Nanomaterials

Lanthanide-Doped Photoluminescence Hollow Structures: Recent Advances and Applications.

Lanthanide-doped nanomaterials have attracted significant attention for their preeminent properties and widespread applications. Due to the unique characteristic, the lanthanide-doped photoluminescence materials with hollow structures may provide advantages including enhanced light harvesting, intensified electric field density, improved luminescent property, and larger drug loading capacity. Herein, the synthesis, properties, and applications of lanthanide-doped photoluminescence hollow structures (LPHSs) are comprehensively reviewed. First, different strategies for the engineered synthesis of LPHSs are described in detail, which contain hard, soft, self-templating methods and other techniques. Thereafter, the relationship between their structure features and photoluminescence properties is discussed. Then, niche applications including biomedicines, bioimaging, therapy, and energy storage/conversion are focused on and superiorities of LPHSs for these applications are particularly highlighted. Finally, keen insights into the challenges and personal prospects for the future development of the LPHSs are provided.

Understanding the Role of Yb3+ in the Nd/Yb Coupled 808-nm-Responsive Upconversion.

The realization of upconversion at 808 nm excitation has shown great advantages in advancing the broad bioapplications of lanthanide-doped nanomaterials. In an 808 nm responsive system, Nd3+ and Yb3+ are both needed where Nd3+ acts as a sensitizer through absorbing the excitation irradiation. However, few studies have been dedicated to the role of Yb3+. Here, we report a systemic investigation on the role of Yb3+ by designing a set of core-shell-based nanostructures. We find that energy migration over the ytterbium sublattice plays a key role in facilitating the energy transportation, and moreover, we show that the interfacial energy transfer occurring at the core-shell interface also has a contribution to the upconversion. By optimizing the dopant concentration and surface anchoring the infrared indocyanine green dye, the 808 nm responsive upconversion is markedly enhanced. These results present an in-depth understanding of the fundamental interactions among lanthanides, and more importantly, they offer new possibilities to tune and control the upconversion of lanthanide-based luminescent materials.

Impact of Lanthanide Nanomaterials on Photonic Devices and Smart Applications.

Half a century after its initial emergence, lanthanide photonics is facing a profound remodeling induced by the upsurge of nanomaterials. Lanthanide-doped nanomaterials hold promise for bioapplications and photonic devices because they ally the unmatched advantages of lanthanide photophysical properties with those arising from large surface-to-volume ratios and quantum confinement that are typical of nanoobjects. Cutting-edge technologies and devices have recently arisen from this association and are in turn promoting nanophotonic materials as essential tools for a deeper understanding of biological mechanisms and related medical diagnosis and therapy, and as crucial building blocks for next-generation photonic devices. Here, the recent progress in the development of nanomaterials, nanotechnologies, and nanodevices for clinical uses and commercial exploitation is reviewed. The candidate nanomaterials with mature synthesis protocols and compelling optical uniqueness are surveyed. The specific fields that are directly driven by lanthanide doped nanomaterials are emphasized, spanning from in vivo imaging and theranostics, micro-/nanoscopic techniques, point-of-care medical testing, forensic fingerprints detection, to micro-LED devices.

Quantum control and enhancement of multi-color emissions in upconversion nanoparticles

Upconversion luminescence (UCL) of lanthanide-doped nanomaterials is usually a low-efficiency nonlinear process, involving multi-step, multi-channel transitions in a multi-level system. Here, we demonstrate quantum control and enhancement of multi-color (e.g., red and green) UCLs of NaYF4:Yb3+/Er3+ nanoparticles with metallic Fabry-Perot micro-cavities. Besides realization of controlled single-color UCLs, their internal quantum efficiencies are strongly enhanced, up to 3–4 orders of times. Experimental results indicate that the controlled single-color UCLs and enhancements are caused not only by modifications of the spontaneous radiation rates for the red- and green-color transitions but also by influencing the intermediate transitions to result in modified distributions of electrons in each of the multiple Er3+ levels, facilitating emission of either red- or green-color light. This work suggests a way to control photon emissions in systems with multi-channel transitions and/or multi-step excitations.

Alleviating Luminescence Concentration Quenching in Upconversion Nanoparticles through Organic Dye Sensitization.

The phenomenon of luminescence concentration quenching exists widely in lanthanide-based luminescent materials, setting a limit on the content of lanthanide emitter that can be used to hold the brightness. Here, we introduce a concept involving energy harvesting by a strong absorber and subsequent energy transfer to a lanthanide that largely alleviates concentration quenching. We apply this concept to Nd3+ emitters, and we show both experimentally and theoretically that the optimal doping concentration of Nd3+ in colloidal NaYF4:Nd upconverting nanoparticles is increased from 2 to 20 mol% when an energy harvestor organic dye (indocyanine green, ICG) is anchored onto the nanoparticle surface, resulting in ∼10 times upconversion brightness. Theoretical analysis indicated that a combination of efficient photon harvesting due to the large absorption cross section of ICG (∼30 000 times higher than that of Nd3+), non-radiative energy transfer (efficiency ∼57%) from ICG to the surface bound Nd3+ ions, and energy migration among the Nd3+ ions was able to activate Nd3+ ions inside the nanoparticle at a rate comparable with that of the pronounced short-range quenching interaction at elevated Nd3+ concentrations. This resulted in the optimal concentration increase to produce significantly enhanced brightness. Theoretical modeling shows a good agreement with the experimental observation. This strategy can be utilized for a wide range of other lanthanide-doped nanomaterials being utilized for bioimaging and solar cell applications.

Nd3+-Sensitized Upconversion Nanophosphors: EfficientIn VivoBioimaging Probes with Minimized Heating Effect

Upconversion (UC) process in lanthanide-doped nanomaterials has attracted great research interest for its extensive biological applications in vitro and in vivo, benefiting from the high tissue penetration depth of near-infrared excitation light and low autofluorescence background. However, the 980 nm laser, typically used to trigger the Yb(3+)-sensitized UC process, is strongly absorbed by water in biological structures and could cause severe overheating effect. In this article, we report the extension of the UC excitation spectrum to shorter wavelengths, where water has lower absorption. This is realized by further introducing Nd(3+) as the sensitizer and by building a core/shell structure to ensure successive Nd(3+) → Yb(3+) → activator energy transfer. The efficacy of this Nd(3+)-sensitized UC process is demonstrated in in vivo imaging, and the results confirmed that the laser-induced local overheating effect is greatly minimized.