Dynamic modulation of multicolor upconversion luminescence of Er3+ via excitation pulse width.

Lanthanide-doped upconversion (UC) luminescent materials display multicolor emissions, making them ideal for a variety of applications, such as multi-channel biological imaging, fluorescence encryption, anti-counterfeiting, and 3D display. Manipulating the UC emissions of the luminescent materials with a fixed composition is crucial for their applications. Herein, we propose a facile strategy to achieve pulse-width-dependent multicolor UC emissions in NaYF4:Yb/Er/Tm nanocrystals. Upon excitation with a 980 nm continuous-wave laser diode, Er3+ ions in NaYF4:20%Yb,15%Er,1%Tm nanocrystals exhibited UC emissions with a red-to-green (R/G) ratio of 11.3. Nevertheless, by employing a 980 nm pulse laser with pulse widths from 0.1 to 10 ms, the UC R/G ratio can be easily adjusted from 0.9 to 11.3, resulting in continuous and remarkable color transformation from green, yellow, orange, to red. By virtue of the dynamic luminescence color variation of these NaYF4:20%Yb,15%Er,1%Tm nanocrystals, we demonstrated their potential applications in the areas of anti-counterfeiting and information encryption. These findings provide deep insights into the excited-state dynamics and energy transfer of Er3+ in NaYF4:Yb/Er/Tm nanocrystals upon 980 nm pulse excitation, which may pave the way for designing multicolor UC materials toward versatile applications.

Near-Infrared Nanophosphors Based on CuInSe2 Quantum Dots with Near-Unity Photoluminescence Quantum Yield for Micro-LEDs Applications.

Highly efficient near-infrared (NIR) luminescent nanomaterials are urgently required for portable mini or micro phosphors-converted light-emitting diodes (pc-LEDs). However, most existing NIR-emitting phosphors are generally restricted by their low photoluminescence (PL) quantum yield (QY) or large particle size. Herein, a kind of highly efficient NIR nanophosphors is developed based on copper indium selenide quantum dots (CISe QDs). The PL peak of these QDs can be exquisitely manipulated from 750 to 1150 nm by altering the stoichiometry of Cu/In and doping with Zn2+ . Their absolute PLQY can be significantly improved from 28.6% to 92.8% via coating a ZnSe shell. By combining the phosphors with a commercial blue chip, an NIR pc-LED is fabricated with remarkable photostability and a record-high radiant flux of 88.7 mW@350 mA among the Pb/Cd-free QDs-based NIR pc-LEDs. Particularly, such QDs-based nanophosphors acted as excellent luminescence converter for NIR micro-LEDs with microarray diameters below 5 µm, which significantly exceeds the resolutions of current commercial inkjet display pixels. The findings may open new avenues for the exploration of highly efficient NIR micro-LEDs in a variety of applications.

Ultrasensitive Urinary Diagnosis of Organ Injuries Using Time-Resolved Luminescent Lanthanide Nano-bioprobes.

Urinary sensing of synthetic biomarkers that are released into urine after specific activation in an in vivo disease environment is an emerging diagnosis strategy to overcome the insensitivity of a previous biomarker assay. However, it remains a great challenge to achieve sensitive and a specific urinary photoluminescence (PL) diagnosis. Herein, we report a novel urinary time-resolved PL (TRPL) diagnosis strategy by exploiting europium complexes of diethylenetriaminepentaacetic acid (Eu-DTPA) as synthetic biomarkers and designing the activatable nanoprobes. Notably, TRPL of Eu-DTPA in the enhancer can eliminate the urinary background PL for ultrasensitive detection. We achieved sensitive urinary TRPL diagnosis of mice kidney and liver injuries by using simple Eu-DTPA and Eu-DTPA-integrated nanoprobes, respectively, which cannot be realized by traditional blood assays. This work demonstrates the exploration of lanthanide nanoprobes for in vivo disease-activated urinary TRPL diagnosis for the first time, which might advance the noninvasive diagnosis of diverse diseases via tailorable nanoprobe designs.

Unveiling Local Electronic Structure of Lanthanide-Doped Cs2 NaInCl6 Double Perovskites for Realizing Efficient Near-Infrared Luminescence.

Lanthanide ion (Ln3+ )-doped halide double perovskites (DPs) have evoked tremendous interest due to their unique optical properties. However, Ln3+ ions in these DPs still suffer from weak emissions due to their parity-forbidden 4f-4f electronic transitions. Herein, the local electronic structure of Ln3+ -doped Cs2 NaInCl6 DPs is unveiled. Benefiting from the localized electrons of [YbCl6 ]3- octahedron in Cs2 NaInCl6 DPs, an efficient strategy of Cl- -Yb3+ charge transfer sensitization is proposed to obtain intense near-infrared (NIR) luminescence of Ln3+ . NIR photoluminescence (PL) quantum yield (QY) up to 39.4% of Yb3+ in Cs2 NaInCl6 is achieved, which is more than three orders of magnitude higher than that (0.1%) in the well-established Cs2 AgInCl6 via conventional self-trapped excitons sensitization. Density functional theory calculation and Bader charge analysis indicate that the [YbCl6 ]3- octahedron is strongly localized in Cs2 NaInCl6 :Yb3+ , which facilitates the Cl- -Yb3+ charge transfer process. The Cl- -Yb3+ charge transfer sensitization mechanism in Cs2 NaInCl6 :Yb3+ is further verified by temperature-dependent steady-state and transient PL spectra. Furthermore, efficient NIR emission of Er3+ with the NIR PLQY of 7.9% via the Cl- -Yb3+ charge transfer sensitization is realized. These findings provide fundamental insights into the optical manipulation of Ln3+ -doped halide DPs, thus laying a foundation for the future design of efficient NIR-emitting DPs.

Polarity-dependent emission from hydroxyl-free carbon nanodots.

Surface groups of carbon nanodots (CNDs) play a key role in modulating their photoluminescence (PL) properties. However, most of the as-prepared CNDs are complex mixtures of CNDs bearing different surface groups. Thus, the purification of CNDs is essential to reveal the PL mechanism of CNDs. Herein, we present a facile method to synthesize hydroxyl (-OH) free CNDs, followed by intelligently guided column chromatographic separation of CNDs with specific functional groups according to their degree of polarity. After systematic investigation of the separated non-polar CNDs (NP-CNDs) and polar CNDs (P-CNDs), it is revealed that radiative photon emission dominates in the NP-CNDs, which exhibits excitation wavelength-independent emissions. In contrast, an increase in the solvent polarity of P-CNDs improves Frank-Condon excited state stabilization to achieve excitation wavelength-dependent emissions. In particular, white-light emitting P-CNDs with CIE coordinates of (0.332, 0.336) are produced. These findings provide new insights into the nature of the PL mechanism for CNDs, which may pave the way towards the rational design of highly efficient and emission tunable CNDs for various applications.

Boosting Near-Infrared Luminescence of Lanthanide in Cs2 AgBiCl6 Double Perovskites via Breakdown of the Local Site Symmetry.

Currently, lanthanide (Ln3+ )-doped near-infrared (NIR)-emitting double perovskites (DPs) suffer from low photoluminescence quantum yield (PLQY). Herein, we develop a new class of NIR-emitting DPs based on Ln3+ -doped Cs2 (Na/Ag)BiCl6 . Benefiting from the Na+ -induced breakdown of local site symmetry in the Cs2 AgBiCl6 DPs, effective NIR emissions of Ln3+ are realized through Bi3+ sensitization. Specifically, 7.3-fold and 362.9-fold enhanced NIR emissions of Yb3+ and Er3+ are achieved in Cs2 Ag0.2 Na0.8 BiCl6 DPs relative to those in Na-free Cs2 AgBiCl6 counterparts, respectively. The optimal absolute NIR PLQYs for Yb3+ and Er3+ in Cs2 Ag0.2 Na0.8 BiCl6 DPs are determined to be 19.0 % and 4.3 %, respectively. Raman spectroscopy and first-principles density functional theory calculations verify the sublattice distortion in Cs2 (Na/Ag)BiCl6 DPs via Na+ doping. These findings provide fundamental insights into the design of efficient NIR-emitting Ln3+ -doped DPs for versatile optoelectronic applications.

Thermally boosted upconversion and downshifting luminescence in Sc2(MoO4)3:Yb/Er with two-dimensional negative thermal expansion.

Rare earth (RE3+)-doped phosphors generally suffer from thermal quenching, in which their photoluminescence (PL) intensities decrease at high temperatures. Herein, we report a class of unique two-dimensional negative-thermal-expansion phosphor of Sc2(MoO4)3:Yb/Er. By virtue of the reduced distances between sensitizers and emitters as well as confined energy migration with increasing the temperature, a 45-fold enhancement of green upconversion (UC) luminescence and a 450-fold enhancement of near-infrared downshifting (DS) luminescence of Er3+ are achieved upon raising the temperature from 298 to 773 K. The thermally boosted UC and DS luminescence mechanism is systematically investigated through in situ temperature-dependent Raman spectroscopy, synchrotron X-ray diffraction and PL dynamics. Moreover, the luminescence lifetime of 4I13/2 of Er3+ in Sc2(MoO4)3:Yb/Er displays a strong temperature dependence, enabling luminescence thermometry with the highest relative sensitivity of 12.3%/K at 298 K and low temperature uncertainty of 0.11 K at 623 K. These findings may gain a vital insight into the design of negative-thermal-expansion RE3+-doped phosphors for versatile applications.

Boosting the Self-Trapped Exciton Emission in Alloyed Cs2 (Ag/Na)InCl6 Double Perovskite via Cu+ Doping.

Fundamental understanding of the effect of doping on the optical properties of 3D double perovskites (DPs) especially the dynamics of self-trapped excitons (STEs) is of vital importance for their optoelectronic applications. Herein, a unique strategy via Cu+ doping to achieve efficient STE emission in the alloyed lead-free Cs2 (Ag/Na)InCl6 DPs is reported. A small amount (1.0 mol%) of Cu+ doping results in boosted STE emission in the crystals, with photoluminescence (PL) quantum yield increasing from 19.0% to 62.6% and excitation band shifting from 310 to 365 nm. Temperature-dependent PL and femtosecond transient absorption spectroscopies reveal that the remarkable PL enhancement originates from the increased radiative recombination rate and density of STEs, as a result of symmetry breakdown of the STE wavefunction at the octahedral Ag+ site. These findings provide deep insights into the STE dynamics in Cu+ -doped Cs2 (Ag/Na)InCl6 , thereby laying a foundation for the future design of new lead-free DPs with efficient STE emission.

Highly efficient NIR-II luminescent I-III-VI semiconductor nanoprobes based on AgInTe2:Zn/ZnS nanocrystals.

Highly efficient luminescence of AgInTe2:Zn/ZnS nanocrystals with the maximum NIR-II quantum yield of 25.2% has been designed through elaborately manipulating the structure to reduce their internal and surface defects. These AgInTe2:Zn/ZnS nanoprobes were employed for sensitive homogeneous biodetection of xanthine oxidase with the limit of detection down to 25 nU L-1.

Tumor-Microenvironment-Responsive Biodegradable Nanoagents Based on Lanthanide Nucleotide Self-Assemblies toward Precise Cancer Therapy.

Stimuli-responsive nanoagents, which simultaneously satisfy normal tissue clearance and tumor-specific responsive treatment, are highly attractive for precise cancer theranostics. Herein, we develop a unique template-induced self-assembly strategy for the exquisitely controlled synthesis of self-assembled lanthanide (Ln3+ ) nucleotide nanoparticles (LNNPs) with amorphous structure and tunable size from sub-5 nm to 105 nm. By virtue of the low-temperature (10 K) and high-resolution spectroscopy, the local site symmetry of Ln3+ in LNNPs is unraveled for the first time. The proposed LNNPs are further demonstrated to possess the ability for highly efficient loading and tumor-microenvironment-responsive release of doxorubicin. Particularly, sub-5 nm LNNPs not only exhibit excellent biocompatibility and predominant renal-clearance performance, but also enable efficient tumor retention. These findings reveal the great potential of LNNPs as a new generation of therapeutic platform to overcome the dilemma between efficient therapy and long-term toxicity of nanoagents for future clinical applications.

Enhancing Dye-Triplet-Sensitized Upconversion Emission Through the Heavy-Atom Effect in CsLu2 F7 :Yb/Er Nanoprobes.

Lanthanide (Ln3+ )-doped upconversion (UC) nanoprobes, which have drawn extensive attention for various bioapplications, usually suffer from small absorption cross-sections and weak luminescence intensity of Ln3+ ions. Herein, we report the controlled synthesis of a new class of Ln3+ -doped UC nanoprobes based on CsLu2 F7 :Yb/Er nanocrystals (NCs), which can effectively increase the intersystem crossing (ISC) efficiency from singlet excited state to triplet excited state of IR808 up to 99.3 % through the heavy atom effect. By virtue of the efficient triplet sensitization of IR808, the optimal UC luminescence (UCL) intensity of IR808-modified CsLu2 F7 :Yb/Er NCs is enhanced by 1309 times upon excitation at 808 nm. Benefiting from the intense dye-triplet-sensitized UCL, the nanoprobes are demonstrated for sensitive assay of extracellular and intracellular hypochlorite with an 808-nm/980-nm dual excited ratiometric strategy.

Unusual Temperature Dependence of Bandgap in 2D Inorganic Lead-Halide Perovskite Nanoplatelets.

Understanding the origin of temperature-dependent bandgap in inorganic lead-halide perovskites is essential and important for their applications in photovoltaics and optoelectronics. Herein, it is found that the temperature dependence of bandgap in CsPbBr3 perovskites is variable with material dimensionality. In contrast to the monotonous redshift ordinarily observed in bulk-like CsPbBr3 nanocrystals (NCs), the bandgap of 2D CsPbBr3 nanoplatelets (NPLs) exhibits an initial blueshift then redshift trend with decreasing temperature (290-10 K). The Bose-Einstein two-oscillator modeling manifests that the blueshift-redshift crossover of bandgap in the NPLs is attributed to the significantly larger weight of contribution from electron-optical phonon interaction to the bandgap renormalization in the NPLs than in the NCs. These new findings may gain deep insights into the origin of bandgap shift with temperature for both fundamentals and applications of perovskite semiconductor materials.

The effect of surface-capping oleic acid on the optical properties of lanthanide-doped nanocrystals.

The rapid development of nanotechnology has placed a higher demand on the synthesis of nanomaterials. Benefiting from its capability to keep nanoparticles away from aggregation, oleic acid (OA) has been routinely utilized as a capping agent in the synthesis of monodisperse nanocrystals. To satisfy downstream biological applications, hydrophobic OA capping on the surface should be removed or coated, but scarce attention has been paid to its influence on the optical properties of nanocrystals. In this work, the effect of surface-capping OA has been systematically explored on the optical properties of lanthanide-doped upconversion and downshifting nanocrystals, respectively. The emission intensity and lifetime of emissive lanthanides have been compared between OA-capped and ligand-free nanocrystals either in solid state or in colloidal solution. In solid state, surface-capping OA can significantly influence both emission intensity and radiative transition possibility of emissive lanthanides. However, in colloidal solution, a distinct variation between OA-capped and ligand-free nanocrystals is observed. Besides, the effect of OA on the luminescence dynamics of lanthanides with different energy gaps (emitting level to the next-lower-energy level) has been investigated in colloidal solution. The possible mechanism for the effect of OA on the optical properties of lanthanide-doped nanocrystals has been further proposed.

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.

Ultrasensitive Point-of-Care Test for Tumor Marker in Human Saliva Based on Luminescence-Amplification Strategy of Lanthanide Nanoprobes.

The point-of-care detection of tumor markers in saliva with high sensitivity and specificity remains a daunting challenge in biomedical research and clinical applications. Herein, a facile and ultrasensitive detection of tumor marker in saliva based on luminescence-amplification strategy of lanthanide nanoprobes is proposed. Eu2O3 nanocrystals are employed as bioprobes, which can be easily dissolved in acidic enhancer solution and transform into a large number of highly luminescent Eu3+ micelles. Meanwhile, disposable syringe filter equipped with nitrocellulose membrane is used as bioassay platform, which facilitates the accomplishment of detection process within 10 min. The rational integration of dissolution enhanced luminescent bioassay strategy and miniaturized detection device enables the unique lab-in-syringe assay of tumor marker like carcinoembryonic antigen (CEA, an important tumor marker in clinic diagnosis and prognosis of cancer) with a detection limit down to 1.47 pg mL-1 (7.35 × 10-15 m). Upon illumination with a portable UV flashlight, the photoluminescence intensity change above 0.1 ng mL-1 (0.5 × 10-12 m) of CEA can be visually detected by naked eyes, which allows one to qualitatively evaluate the CEA level. Moreover, we confirm the reliability of using the amplified luminescence of Eu2O3 nanoprobes for direct quantitation of CEA in patient saliva samples, thus validates the practicality of the proposed strategy for both clinical diagnosis and home self-monitoring of tumor marker in human saliva.

Colloidal Alloyed Quantum Dots with Enhanced Photoluminescence Quantum Yield in the NIR-II Window.

Semiconductor quantum dots (QDs) with photoluminescence (PL) emission at 900-1700 nm (denoted as the second near-infrared window, NIR-II) exhibit much-depressed photon absorption and scattering, which has stimulated extensive researches in biomedical imaging and NIR devices. However, it is very challenging to develop NIR-II QDs with a high photoluminescence quantum yield (PLQY) and excellent biocompatibility. Herein, we designed and synthesized an alloyed silver gold selenide (AgAuSe) QD with a bright emission from 820 to 1170 nm and achieved a record absolute PLQY of 65.3% at 978 nm emission among NIR-II QDs without a toxic element and a long lifetime of 4.58 µs. It is proved that the high PLQY and long lifetime are mainly attributed to the prevented nonradiative transition of excitons, probably resulted from suppressing cation vacancies and crystal defects from the high mobility of Ag ions by alloying Au atoms. These high-PLQY QDs with nontoxic heavy metal exhibit great application potential in bioimaging, light emitting diodes (LEDs), and photovoltaic devices.

Engineering the Bandgap and Surface Structure of CsPbCl3 Nanocrystals to Achieve Efficient Ultraviolet Luminescence.

Herein, we report the design of novel ultraviolet luminescent CsPbCl3 nanocrystals (NCs) with the emission peak at 381 nm through doping of cadmium ions. Subsequently, a surface passivation strategy with CdCl2 is adopted to improve their photoluminescence quantum yield (PLQY) with the maximum value of 60.5 %, which is 67 times higher than that of the pristine counterparts. The PLQY of the surface passivated NCs remains over 50 % after one week while the pristine NCs show negligible emission. By virtue of density functional theory calculations, we reveal that the higher PLQY and better stability after surface passivation may result from the significant elimination of surface chloride vacancy (VCl ) defects. These findings provide fundamental insights into the optical manipulation of metal ion-doped CsPbCl3 NCs.

Recent advances in design of lanthanide-containing NIR-II luminescent nanoprobes.

Luminescent biosensing in the second near-infrared window (NIR-II, 1000-1700 nm) region, which has weak tissue scattering and low autofluorescence, draws extensive attention owing to its deep tissue penetration, good spatial resolution and high signal-to-background ratio. As a new generation of NIR-II probes, lanthanide (Ln3+)-containing nanoprobes exhibit several superior properties. With the rapid development of Ln3+-containing NIR-II nanoprobes, many significant advances have been accomplished in their optical properties tuning and surface functional modification for further bioapplications. Rather than being exhaustive, this review aims to survey the recent advances in the design strategies of inorganic Ln3+-containing NIR-II luminescent nanoprobes by highlighting their optical performance optimization and surface modification approaches. Moreover, challenges and opportunities for this kind of novel NIR-II nanoprobes are envisioned.

One-Step Transformation from Rofecoxib to a COX-2 NIR Probe for Human Cancer Tissue/Organoid Targeted Bioimaging.

COX-2 fluorescent probes are promising tools for cancer diagnosis. Such probes have been conventionally designed by conjugating a fluorophore to COX-2 inhibitors through lengthy synthetic processes. Herein, a type of fluorescent probe for COX-2 imaging has been developed using a single-step process from rofecoxib. In total, six rofecoxib analogues were designed using this unique strategy. Several analogues retained comparative COX-2 targeting activity of rofecoxib and also exhibited attractive fluorescent properties, which were investigated using a combination of experimental and theoretical approaches. The most potent analogue, 2a1, displayed strong fluorescent imaging of COX-2 in HeLa cells overexpressing COX-2 compared to Raw 264.7 cells and celecoxib-treated HeLa cells that expressed low levels of COX-2. Notably, our studies indicate that 2a1 can differentiate human cancer tissue from adjacent tissue with much brighter fluorescence either in histological section or cultured 3D organoids. These results illustrate the potential of 2a1 as a COX-2 near infrared fluorescent probe for human cancer imaging in clinical settings.

Energy transfer designing in lanthanide-doped upconversion nanoparticles.

Lanthanide (Ln3+)-doped upconversion nanoparticles (UCNPs), exhibiting excellent optical properties such as long photoluminescence lifetime, narrow emission bandwidth, and low autofluorescence background, have been applied in many fields, especially in biological analysis and medical diagnostics. Despite the exciting progress, the applications of Ln3+-doped UCNPs are hindered by the small absorption cross-section and low upconversion luminescence efficiency of Ln3+. To this regard, several effective strategies associated with energy transfer designing have been proposed to modulate the upconversion luminescence properties of Ln3+ in the past few decades. In this feature article, we focus on the most recent development of optical property designing in Ln3+-doped UCNPs on the basis of energy transfer between Ln3+-Ln3+, Ln3+-dyes, and Ln3+-quantum dots. Some future efforts towards the energy transfer designing in Ln3+-doped UCNPs are also proposed.