ErIII‐Cored Complexes Based on Dendritic PtII–Porphyrin Ligands: Synthesis,Near‐IR Emission Enhancement,and Photophysical Studies

A series of stable and inert complexes with Er^III cores and dendritic Pt^II‐porphyrin ligands exhibit strong near‐IR (NIR) emission bands via highly efficient energy transfer from the excited triplet state of the Pt^II‐porphyrin ligand to Er³⁺ ions. The NIR emission intensity of thin films of Er^III complexes at 1530 nm, originating from 4f–4f electronic transitions from the first excited state (⁴I_13/2) to the ground state (⁴I_15/2) of the Er³⁺ ion, is dramatically enhanced upon increasing the generation number (n) of the aryl ether dendrons because of site‐isolation and light‐harvesting (LH) effects. Attempts are made to distinguish the site‐isolation effect from the LH effect in these complexes. Surprisingly, the site‐isolation effect is dominant over the LH effect in the Er³⁺‐[Gn‐PtP]₃(terpy) (terpy: 2,2′:6′,2″‐terpyridine) series of complexes, even though the present dendrimer systems with Er^III cores have a proper cascade‐type energy gradient. This might be due to the low quantum yield of the aryl ether dendrons. Thus, the NIR emission intensity of Er³⁺‐[G3‐PtP]₃(terpy) is 30 times stronger than that of Er³⁺‐[G1‐PtP]₃(terpy). The energy transfer efficiency between the Pt^II‐porphyrin moiety in the dendritic Pt^II‐porphyrin ligands and the Ln³⁺ ion increases with increasing generation number of the dendrons from 12–43 %. The time‐resolved luminescence spectra in the NIR region show monoexponential decays with a luminescence lifetime of 0.98 μs for Er³⁺‐[G1‐PtP]₃(terpy), 1.64 μs for Er³⁺‐[G2‐PtP]₃(terpy), and 6.85 μs for Er³⁺‐[G3‐PtP]₃(terpy) in thin films of these complexes. All the Er^III‐cored dendrimer complexes exhibit excellent thermal stability and photostability, and possess good solubility in common organic solvents.     

Effects of Phonon Confinement on Anomalous Thermalization,Energy Transfer,and Upconversion in Ln3+‐Doped Gd2O3 Nanotubes

There is a growing interest in understanding how size‐dependent quantum confinement affects the photoluminescence efficiency, excited‐state dynamics, energy‐transfer and thermalization phenomena in nanophosphors. For lanthanide (Ln³⁺)‐doped nanocrystals, despite the localized 4f states, confinement effects are induced mostly via electron–phonon interactions. In particular, the anomalous thermalization reported so far for a handful of Ln³⁺‐doped nanocrystals has been rationalized by the absence of low‐frequency phonon modes. This nanoconfinement may further impact on the Ln³⁺ luminescence dynamics, such as phonon‐assisted energy transfer or upconversion processes. Here, intriguing and unprecedented anomalous thermalization in Gd₂O₃:Eu³⁺ and Gd₂O₃:Yb³⁺,Er³⁺ nanotubes, exhibiting up to one order of magnitude larger than previously reported for similar materials, is reported. This anomalous thermalization induces unexpected energy transfer from Eu³⁺ C₂ to S₆ crystallographic sites, at 11 K, and ²H_11/2 → ⁴I_15/2 Er³⁺ upconversion emission; it is interpreted on the basis of the discretization of the phonon density of states, easily tuned by varying the annealing temperature (923–1123 K) in the synthesis procedure, and/or the Ln³⁺ concentration (0.16–6.60%).     

Er3+ Sensitized Photon Upconversion Nanocrystals

Lanthanide doped upconversion nanocrystals, showing bright future in diverse fields, are typically excited by ≈700–1000 nm light when Nd³⁺ and Yb³⁺ are used as sensitizers. Thus far, extending the excitation range of upconversion nanocrystals is still a formidable challenge. Herein, a new type of upconversion nanocrystals is reported, using Er³⁺ ions as sensitizers, which can be excited by 1532 nm light located in the second near‐infrared biological window. Through Er³⁺ sensitization, upconversion emission from a series of activators, including Nd³⁺, Ho³⁺, Eu³⁺, and Tm³⁺, is obtained and can be modulated by Yb³⁺ codoping. In addition, Er³⁺ sensitized photon upconversion of Ho³⁺ and Tm³⁺ can be further enhanced by shell coating. It is found that Er³⁺ sensitized upconversion processes are mainly dependent on the energy transfer between Er³⁺ ions and activators. Considering the demonstration of anticounterfeiting by using this newly designed nanocrystal, it is anticipated that these results can bring more opportunities to upconversion nanomaterials in other aspects, ranging from lasing to super resolution imaging.     

A New Sol–Gel Material Doped with an Erbium Complex and Its Potential Optical‐Amplification Application

The crystal structure of a ternary Er(DBM)₃phen complex (DBM = dibenzoylmethane; phen = 1,10‐phenanthroline) and its in‐situ synthesis via a sol–gel process are reported. The infrared (IR), diffuse reflectance (DR), and fluorescence spectra of the pure complex and the Er³⁺/DBM/phen co‐doped luminescent hybrid gel, formed via an in‐situ method (ErDP gel), have been investigated. The results reveal that the erbium complex is successfully synthesized in situ in the ErDP gel. Excitation at the maximum absorption wavelength of the ligands resulted in the typical near‐IR luminescence (centered at around 1.54 μm) resulting from the ⁴I_13/2 → ⁴I_15/2 transition of the Er³⁺ ion, which contributes to the efficient energy transfer from the ligands to the Er³⁺ ion in both the Er(DBM)₃phen complex and the ErDP gel (an antenna effect). The full width at half maximum (FWHM) centered at 1541 nm in the emission spectrum of the ErDP gel is 72 nm, which has potential for optical‐amplification applications. Further theoretical analysis on the Er³⁺ ion in the ErDP gel shows that it appears to be a promising candidate for tunable lasers and planar optical amplifiers.     

Down/Up Conversion in Ln3+‐Doped YF3 Nanocrystals

Nanocrystalline Ln³⁺‐doped YF₃ phosphors have been synthesized via a facile sonochemistry‐assisted hydrothermal route. YF₃ nanoparticles are demonstrated to be a good host material for different lanthanides. Varying the dopants leads to different optical properties. In particular, the feasibility of inducing red, green, and especially blue emission in the Yb³⁺/Er³⁺ co‐doped YF₃ sample by up‐conversion excitation in the near‐infrared region is demonstrated. Such unusually strong 411 nm blue up‐conversion emission has seldom been reported in other Yb³⁺/Er³⁺‐doped systems. The up‐conversion mechanisms have been analyzed.     

Spectral properties and energy transfer in Er3+/Yb3+ co-doped LiYF4 crystal

Laser crystals of LiYF4 (LYF) singly doped with Er3+ in 2.0% and co-doped with Er3+/Yb3+ in about 2.0%/1.0% molar fraction in the raw composition are grown by a vertical Bridgman method. X-ray diffraction (XRD), absorption spectra, fluorescence spectra and decay curves are measured to investigate the structural and luminescent properties of the crystals. Compared with the Er3+ singly doped sample, obviously enhanced emission at 1.5 μm wavelength and green and red up-conversion emissions from Er3+/Yb3+ co-doped crystal are observed under the excitation of 980 nm laser diode. Meanwhile, the emission at 2.7 μm wavelength from Er3+ singly doped crystal is reduced. The fluorescence decay time ranging from 18.60 ms for Er3+ singly doped crystal to 23.01 ms for Er3+/Yb3+ co-doped crystal depends on the ionic concentration. The luminescent mechanisms for the Er3+/Yb3+ co-doped crystals are analyzed, and the possible energy transfer processes from Yb3+ to Er3+ are proposed.     

Atomic‐Level Passivation of Individual Upconversion Nanocrystal for Single Particle Microscopic Imaging

Lanthanide‐doped upconversion nanoparticles (UCNPs) have significant applications for single‐molecule probes and high‐resolution display. However, one of their major hurdles is the weak luminescence, and this remains a grand challenge to achieve at the single‐particle level. Here, 484‐fold luminescence enhancement in LuF₃:Yb³⁺, Er³⁺ rhombic flake UCNPs is achieved, thanks to the Yb³⁺‐mediated local photothermal effect, and their original morphology, size, and good dispersibility are well preserved. These data show that the surface atomic structure of UCNPs as well as transfer from amorphous to ordered crystal structure is modulated by making use of the local photothermal conversion that is generated by the directional absorption of 980 nm light by Yb³⁺ ions. The confocal luminescence images obtained by super‐resolution stimulated emission depletion also show the great enhancement of individual LuF₃:Yb³⁺, Er³⁺ nanoparticles; the high signal‐to‐noise ratio images indicate that the laser treatment technology opens the door for single particle imaging and practical application.     

Plasmonic Dual‐Enhancement and Precise Color Tuning of Gold Nanorod@SiO2 Coupled Core–Shell–Shell Upconversion Nanocrystals

The last decade has witnessed the remarkable research progress of lanthanide‐doped upconversion nanocrystals (UCNCs) at the forefront of promising applications. However, the future development and application of UCNCs are constrained greatly by their underlying shortcomings such as significant nonradiative processes, low quantum efficiency, and single emission colors. Here a hybrid plasmonic upconversion nanostructure consisting of a GNR@SiO₂ coupled with NaGdF₄:Yb³⁺,Nd³⁺@NaGdF₄:Yb³⁺,Er³⁺@NaGdF₄ core–shell–shell UCNCs is rationally designed and fabricated, which exhibits strongly enhanced UC fluorescence (up to 20 folds) and flexibly tunable UC colors. The experimental findings show that controlling the SiO₂ spacer thickness enables readily manipulating the intensity ratio of the Er³⁺ red, green, and blue emissions, thereby allowing us to achieve the emission color tuning from pale yellow to green upon excitation at 808 nm. Electrodynamic simulations reveal that the tunable UC colors are due to the interplay of plasmon‐mediated simultaneous excitation and emission enhancements in the Er³⁺ green emission yet only excitation enhancement in the blue and red emissions. The results not only provide an upfront experimental design for constructing hybrid plasmonic UC nanostructures with high efficiency and color tunability, but also deepen the understanding of the interaction mechanism between the Er³⁺ emissions and plasmon resonances in such complex hybrid nanostructure.     

Electrospinning Preparation and Drug‐Delivery Properties of an Up‐conversion Luminescent Porous NaYF4:Yb3+, Er3+@Silica Fiber Nanocomposite

Up‐conversion (UC) luminescent porous silica fibers decorated with NaYF₄:Yb³⁺, Er³⁺ nanocrystals (NCs) (denoted as NaYF₄:Yb³⁺, Er³⁺@silica fiber) are prepared by the electrospinning process using cationic surfactant P123 as a template. Monodisperse and hydrophobic oleic acid capped β‐NaYF₄: Yb³⁺, Er³⁺ NCs are prepared by thermal decomposition methodology. Then, these NCs are transferred into aqueous solution by employing cetyltrimethylammonium bromide (CTAB) as secondary surfactant. The water‐dispersible β‐NaYF₄:Yb³⁺, Er³⁺ NCs are dispersed into precursor electrospinning solution containing P123 and tetraethyl orthosilicate (TEOS), followed by preparation of precursor fibers via electrospinning. Finally, porous α‐NaYF₄:Yb³⁺, Er³⁺@silica fiber nanocomposites are obtained after annealing the precursor fibers containing β‐NaYF₄:Yb³⁺, Er³⁺ at 550 °C. The as‐prepared α‐NaYF₄:Yb³⁺, Er³⁺@silica fiber possesses porous structure and UC luminescence properties simultaneously. Furthermore, the obtained nanocomposites can be used as a drug delivery host carrier and drug storage/release properties are investigated, using ibuprofen (IBU) as a model drug. The results indicate that the IBU–loaded α‐NaYF₄:Yb³⁺, Er³⁺@silica fiber nanocomposites show UC emission of Er³⁺ under 980 nm NIR laser excitation and a controlled release property for IBU. Meanwhile, the UC emission intensity of IBU–α‐NaYF₄:Yb³⁺, Er³⁺@silica fiber system varies with the released amount of IBU.     

Synthesis of Magnetic,Up‐Conversion Luminescent,and Mesoporous Core–Shell‐Structured Nanocomposites as Drug Carriers

The synthesis (by a facile two‐step sol–gel process), characterization, and application in controlled drug release is reported for monodisperse core–shell‐structured Fe₃O₄@nSiO₂@mSiO₂@NaYF₄: Yb³⁺, Er³⁺/Tm³⁺ nanocomposites with mesoporous, up‐conversion luminescent, and magnetic properties. The nanocomposites show typical ordered mesoporous characteristics and a monodisperse spherical morphology with narrow size distribution (around 80 nm). In addition, they exhibit high magnetization (38.0 emu g^?1, thus it is possible for drug targeting under a foreign magnetic field) and unique up‐conversion emission (green for Yb³⁺/Er³⁺ and blue for Yb³⁺/Tm³⁺) under 980 nm laser excitation even after loading with drug molecules. Drug release tests suggest that the multifunctional nanocomposites have a controlled drug release property. Interestingly, the up‐conversion emission intensity of the multifunctional carrier increases with the released amount of model drug, thus allowing the release process to be monitored and tracked by the change of photoluminescence intensity. This composite can act as a multifunctional drug carrier system, which can realize the targeting and monitoring of drugs simultaneously.     

Luminescence properties of light-emitting diodes based on GaAs with the up-conversion Y<Subscript>2</Subscript>O<Subscript>2</Subscript>S:Er,Yb luminophor

Y₂O₂S luminophors doped with Er³⁺ and Yb³⁺ ions are produced by means of solid-phase synthesis and deposited onto standard AL123A infrared light-emitting diodes. When excited with 940 nm radiation from a light-emitting diode, the structures exhibit intense visible up-conversion luminescence. A maximal brightness of 2340 cd/m² of green and red up-conversion luminescence at corresponding wavelengths around 550 and 600 nm is observed for the Y₂O₂S compound doped with 2 at % Er³⁺ ions and 6 at % Yb³⁺ ions. The ratio of the intensity of green (or red) up-conversion luminescence to the intensity of infrared Stokes luminescence increases with increasing applied voltage. The efficiency of visible emission of the light-emitting diode structures is η = 1.2 lm/W at an applied voltage of 1.5 V.     

Improvement of 1.53 μm emission and energy transfer of Yb3+/Er3+ co-doped tellurite glass and fiber

To improve the 1.53 μm band emission of Er³⁺, the trivalent Yb³⁺ ions were introduced into the Er³⁺ single-doped tellurite glass with composition of TeO₂–ZnO–La₂O₃, a potential gain medium for Er³⁺-doped fiber amplifier (EDFA). The improved effects were investigated from the measured 1.53 μm band and visible band spontaneous emission spectra together with the calculated 1.53 μm band stimulated emission (signal gain) spectra under the excitation of 975 nm laser diode (LD). It was found that Yb³⁺/Er³⁺ co-doping scheme can remarkably improve the visible band up-conversion and the 1.53 μm band fluorescence emission intensity, and meanwhile improves the 1.53 μm band signal gain to some extent, which were attributed to the result of the effective energy transfer of Yb³⁺:²F_5/2 + Er³⁺:⁴I_15/2 → Yb³⁺:²F_7/2 + Er³⁺:⁴I_11/2. The quantitative study of energy transfer mechanism was performed and microscopic energy transfer parameters between the doped rare-earth ions were determined. In addition, the spectroscopic properties of Er³⁺ were also investigated from the measured absorption spectrum according to the Judd–Ofelt theory, and the structure behavior and thermal stability of the prepared tellurite glass were analyzed based on the X-ray diffraction (XRD) and differential scanning calorimeter (DSC) measurements, respectively.     

Novel Sol–Gel Nano‐Glass–Ceramics Comprising Ln3+‐Doped YF3 Nanocrystals: Structure and High Efficient UV Up‐Conversion

Transparent glass‐ceramics containing Ln³⁺‐doped YF₃ nanocrystals are successfully obtained under adequate thermal treatment of precursor sol–gel glasses for the first time, to the best of our knowledge. Precipitation of YF₃ nanocrystals is confirmed by X‐ray diffraction and high‐resolution transmission electron microscopy images. An exhaustive structural analysis is carried out using Eu³⁺ and Sm³⁺ as probe ions of the final local environment in the nano‐structured glass–ceramic. Noticeable changes in luminescence spectra, related to relative intensity and Stark structure of band components, along with remarkably different lifetime values, allow us to discern between ions residing in precipitated YF₃ nanocrystals and those remaining in a glassy environment. A large fraction of optically active ions is efficiently partitioned into nanocrystals of small size, around 11 nm. Moreover, bright and efficient up‐conversion, including very intense high‐energy emissions in the UV range, due to 4‐ and 5‐infrared photon processes, are achieved in Yb³⁺–Tm³⁺ co‐doped samples. Up‐conversion mechanisms are analysed in depth by means of intensity dependence on sensitiser Yb³⁺ concentration and pump power.     

Up‐Conversion Luminescent and Porous NaYF4:Yb3+, Er3+@SiO2 Nanocomposite Fibers for Anti‐Cancer Drug Delivery and Cell Imaging

Up‐conversion (UC) luminescent and porous NaYF₄:Yb³⁺, Er³⁺@SiO₂ nanocomposite fibers are prepared by electrospinning process. The biocompatibility test on L929 fibrolast cells reveals low cytotoxicity of the fibers. The obtained fibers can be used as anti‐cancer drug delivery host carriers for investigation of the drug storage/release properties. Doxorubicin hydrochloride (DOX), a typical anticancer drug, is introduced into NaYF₄:Yb³⁺, Er³⁺@SiO₂ nanocomposite fibers (denoted as DOX‐NaYF₄:Yb³⁺, Er³⁺@SiO₂). The release properties of the drug carrier system are examined and the in vitro cytotoxicity and cell uptake behavior of these NaYF₄:Yb³⁺, Er³⁺@SiO₂ for HeLa cells are evaluated. The release of DOX from NaYF₄:Yb³⁺, Er³⁺@SiO₂ exhibits sustained, pH‐sensitive release patterns and the DOX‐NaYF₄:Yb³⁺, Er³⁺@SiO₂ show similar cytotoxicity as the free DOX on HeLa cells. Confocal microscopy observations show that the composites can be effectively taken up by HeLa cells. Furthermore, the fibers show near‐infrared UC luminescence and are successfully applied in bioimaging of HeLa cells. The results indicate the promise of using NaYF₄:Yb³⁺, Er³⁺@SiO₂ nanocomposite fibers as multi‐functional drug carriers for drug delivery and cell imaging.     

Effectively Utilizing NIR Light Using Direct Electron Injection from Up‐Conversion Nanoparticles to the TiO2 Photoanode in Dye‐Sensitized Solar Cells

TiO₂/NaYF₄:Yb³⁺,Er³⁺ nano‐heterostructures are prepared in situ on the TiO₂ photoanode of dye‐sensitized solar cells (DSCs). Transmission electron microscopy (TEM) and high‐resolution (HR)‐TEM confirm the formation of TiO₂/NaYF₄:Yb³⁺,Er³⁺ nano‐heterostructures. The up‐converted fluorescence spectrum of the photoanode containing the nano‐heterostructure confirms electron injection from NaYF₄:Yb³⁺,Er³⁺ to the condution band (CB) of TiO₂. When using a photoanode containing the nano‐heterostructure in a DSC, the overall efficiency (η) of the device is 17% higher than that of a device without the up‐conversion nanoparticles (UCNPs) and 13% higher than that of a device containing mixed TiO₂ and UCNPs. Nano‐heterostructures of TiO₂/NaYF₄:Yb³⁺,Tm³⁺ and TiO₂/NaYF₄:Yb³⁺,Ho³⁺ can also be prepared in situ on TiO₂ photoanodes. The overall efficiency of the device containing TiO₂/NaYF₄:Yb³⁺,Ho³⁺ nano‐heterostructures is 15% higher than the control device without UCNPs. When nano‐heterostructures of TiO₂/NaYF₄:Yb³⁺,Tm³⁺ are used, the open‐circuit voltage (V_oc) and the short‐circuit current density (J_sc) are all slightly decreased. The effect of the different UCNPs results from the different energy levels of Er³⁺, Tm³⁺, and Ho³⁺. These results demonstrate that utilizing the UCNPs with the apporpriate energy levels can lead to effective electron injection from the UCNPs to the CB of TiO₂, effectively improving the photocurrent and overall efficiency of DSCs while using NIR light.     

Highly Emissive Nd3+‐Sensitized Multilayered Upconversion Nanoparticles for Efficient 795 nm Operated Photodynamic Therapy

Photodynamic therapy (PDT) is a noninvasive and site‐specific therapeutic technique for the clinical treatment of various of superficial diseases. In order to tuning the operation wavelength and improve the tissue penetration of PDT, rare‐earth doped upconversion nanoparticles (UCNPs) with strong anti‐stokes emission are introduced in PDT recently. However, the conventional Yb³⁺‐sensitized UCNPs are excited at 980 nm which is overlapped with the absorption of water, thus resulting in strong overheating effect. Herein, a convenient but effective design to obtain highly emissive 795 nm excited Nd³⁺‐sensitized UCNPs (NaYF₄:Yb,Er@NaYF₄:Yb_0.1Nd_0.4@NaYF₄) is reported, which provides about six times enhanced upconversion luminescence, comparing with traditional UCNPs (NaYF₄:Yb,Er@NaYF₄). A colloidal stable and non‐leaking PDT nanoplatform is fabricated later through a highly PEGylated mesoporous silica layer with covalently linked photosensitizer (Rose Bengal derivative). With as‐prepared Nd³⁺‐sensitized UCNPs, the nanoplatform can produce singlet oxygen more effective than traditional UCNPs. Significant higher penetration depth and lower overheating are demonstrated as well. All these features make as‐prepared nanocomposites excellent platform for PDT treatment. In addition, the nanoplatform with uniform size, high surface area, and excellent colloidal stability can be extended for other biomedical applications, such as imaging probes, biosensors, and drug delivery vehicles.     

Solution‐Processable Near‐Infrared–Responsive Composite of Perovskite Nanowires and Photon‐Upconversion Nanoparticles

Organolead halide perovskites (OHPs) have shown unprecedented potentials in optoelectronics. However, the inherent large bandgap has restrained its working wavelength within 280–800 nm, while light at other regions, e.g., near‐infrared (NIR), may cause drastic thermal heating effect that goes against the duration of OHP devices, if not properly exploited. Herein, a solution processable and large‐scale synthesis of multifunctional OHP composites containing lanthanide‐doped upconversion nanoparticles (UCNPs) is reported. Upon NIR illumination, the upconverted photons from UCNPs at 520–550 nm can be efficiently absorbed by closely surrounded OHP nanowires (NWs) and photocurrent is subsequently generated. The narrow full width at half maximum of the absorption of rare earth ions (Yb³⁺ and Er³⁺) has ensured high‐selective NIR response. Lifetime characterizations have suggested that Förster resonance energy transfer with an efficiency of 28.5% should be responsible for the direct energy transfer from UCNPs to OHP NWs. The fabricated proof‐of‐concept device has showcased perfect response to NIR light at 980 and 1532 nm, which has paved new avenues for applications of such composites in remote control, distance measurement, and stealth materials.     

Pr3+‐ and Pr3+/Er3+‐Doped Selenide Glasses for Potential 1.6 μm Optical Amplifier Materials

1.6 µm emission originated from Pr³⁺: (³F₃, ³F₄) → ³H₄ transition in Pr³⁺‐ and Pr³⁺/Er³⁺‐doped selenide glasses was investigated under an optical pump of a conventional 1480 nm laser diode. The measured peak wavelength and full‐width at half‐maximum of the fluorescent emission are ~1650 nm and ~120 nm, respectively. A moderate lifetime of the thermally coupled upper manifolds of ~212 ± 10 µs together with a high stimulated emission cross‐section of ~(3 ± 1)×10^??20 cm² promises to be useful for 1.6 µm band fiber‐optic amplifiers that can be pumped with an existing high‐power 1480 nm laser diode. Codoping Er³⁺ enhances the emission intensity by way of a nonradiative Er³+: ⁴I_{13/2 →} Pr³⁺: (³F₃, ³F₄) energy transfer. The Dexter model based on the spectral overlap between donor emission and acceptor absorption describes well the energy transfer from Er³⁺ to Pr³⁺ in these glasses. Also discussed in this paper are major transmission loss mechanisms of a selenide glass optical fiber.     

The Active‐Core/Active‐Shell Approach: A Strategy to Enhance the Upconversion Luminescence in Lanthanide‐Doped Nanoparticles

Nanoparticles of NaGdF₄ doped with trivalent erbium (Er³⁺) and ytterbium (Yb³⁺) are prepared by a modified thermal decomposition synthesis from trifluoroacetate precursors in 1‐octadecene and oleic acid. The nanoparticles emit visible upconverted luminescence on excitation with near‐infrared light. To minimize quenching of this luminescence by surface defects and surface‐associated ligands, the nanoparticles are coated with a shell of NaGdF₄. The intensity of the upconversion luminescence is compared for nanoparticles that were coated with an undoped shell (inert shell) and similar particles coated with a Yb³⁺‐doped shell (active shell). Luminescence is also measured for nanoparticles lacking the shell (core only), and doped with Yb³⁺ at levels corresponding to the doped and undoped core/shell materials respectively. Upconversion luminescence was more intense for the core/shell materials than for the uncoated nanoparticles, and is greatest for the materials having the “active” doped shell. Increasing the Yb³⁺ concentration in the “core‐only” nanoparticles decreases the upconversion luminescence intensity. The processes responsible for the upconversion are presented and the potential advantages of “active‐core”/“active‐shell” nanoparticles are discussed.     

Monovalent Charge Compensation Enables Efficient Lanthanide-Based Near-Infrared Perovskite LEDs

Lanthanide ions (Yb³⁺ or Er³⁺) alloying of CsPb(Cl_1-xBr_x)₃ quantum dots (QDs) to emit approaching 1000 nm show promise in near-infrared light-emitting diodes (NIR-LEDs). High Yb³⁺ alloying ratio increases the electroluminance efficiency of emission at 990 nm and enables high external quantum efficiency (EQE) of NIR-LEDs, however, the high alloying ratio also results in inferior material stability and PLQY drop because of Yb³⁺-induced nanocrystal precipitation. This study finds that the heavy alloying of Yb³⁺ ions causes lattice distortion and coherent energy reduction of Yb³⁺: CsPb(Cl_1-xBr_x)₃ QDs, induced by two Yb³⁺ ions replacing three Pb²⁺, which leads to the collapse of the octahedral structure in ambient conditions. It posits that spontaneous monovalent ion (Na⁺) alloying can address the trade-off between material stability and emission intensity. The Na⁺ occupies the vacancy of Pb²⁺ ions, relaxing the distortion in the lattice and improving the phase stability of octahedral structure, and this optimized structure in turn allows a higher Yb³⁺ alloying ratio. Stability measurements show that the Na⁺/Yb³⁺ co-alloyed films show ten-fold higher material stability and 2.0-fold emission efficiency related to controls. It reports that as a result Na⁺/Yb³⁺ co-alloyed NIR-LEDs have an EQE of 6.4% at 990 nm, which is among the highest perovskite NIR-LEDs beyond 950 nm.