Thermal activation induced charge transfer state absorption redshift realizes strong anti-thermal quenching in Pr3+-activated phosphor.

In our work, a totally anomalous thermal quenching phenomenon of red-shifted and enhanced charge transfer state (CTS) absorption is found for the first time in LiTaO3:xPr3+ phosphors. The crystal structure, luminescent properties and the mechanism of abnormal thermal quenching were investigated in detail.

Development of a novel Eu2+ activated oxonitridosilicate cyan phosphor for enhancing the color quality of a violet-chip-based white LED.

Cyan phosphors are urgently needed to fill the cyan gap and improve the spectral continuity of white light-emitting diodes (LEDs) to cater to the high demand for high-quality lighting. Here, a series of new Eu2+-activated La3Si6.5Al1.5N9.5O5.5 (LSANO) cyan phosphors were prepared, and their luminescence properties and color centers were analyzed through fluorescence spectral measurements from 7 K to 475 K. At 300 K, the photoluminescence excitation (PLE) spectrum monitored at 483 nm presents a broadband of 200-460 nm with a peak at 398 nm, matching well with commercial violet LED chips. When excited by 398 nm violet light, the photoluminescence emission (PL) spectrum of LSANO:0.01Eu2+ exhibits a cyan emission band at about 483 nm. At 7 K, the emission spectrum clearly shows an asymmetric emission band and the emission peak wavelength changes from 483 nm (300 K) to 500 nm (7 K), indicating that there are two possible color centers in the LSANO:Eu2+ phosphor. Moreover, the maximum emission value can be adjusted from 480 to 499 nm by adjusting the doping content of Eu2+. Finally, a violet-chip-based white LED with the optimized color quality of Ra = 91.4, Rf = 90.1, and Rg = 93.6 was fabricated by adding the prepared cyan phosphor, verifying the potential application of the prepared cyan phosphor LSANO:Eu2+ in high-quality white LEDs.

Tuning of the thermal quenching performance of Bi3+-doped scheelite Ca(Mo/W)O4 solid solution phosphors.

The utilization of phosphor materials has always been a significant challenge in terms of improving thermal quenching performance. In this work, the thermal quenching performance tuning mechanism which establishes the band gap and thermal quenching correlation patterns is proposed. The crystal field splitting energy Dq was decreased by changing the surrounding crystal lattice environment of Bi3+ through a solid solution replacement, and the thermal quenching activation energy ΔE of Bi3+ was tuned from 0.117 eV to 0.182 eV accordingly. At 423 K, the luminous intensity increases from 0.101 to 0.396 of the preliminary intensity at 303 K with increasing substitution. In addition, the band gap value of Bi3+ calculated by diffuse reflectance spectroscopy increased from 4.40 eV to 4.72 eV, which corresponds to a linear positive correlation between the band gap and the thermal quenching properties. Furthermore, a monophase white-emitting phosphor with good thermal stability was prepared by constructing a Bi3+-Eu3+ co-doping system. In particular, the relative sensitivity of Sr for temperature measurement applications reached 3.17% K-1 based on the double-luminescence fluorescence intensity ratio. Thus, this modulation scheme can be used as a reference for the design of various phosphor materials with tunable thermal quenching properties in the future.

Thermal Quenching Mechanism of Metal-Metal Charge Transfer State Transition Luminescence Based on Double-Band-Gap Modulation.

Bi3+-related metal-to-metal charge transfer (MMCT) transition phosphors are expected to become a new class of solid-state luminescent materials due to their unique broadband long-wavelength emission; however, the main obstacle to their application is the thermal quenching effect. In this study, one novel thermal quenching mechanism of Bi3+-MMCT transition luminescence is proposed by introducing electron-transfer potential energy (ΔET). Y0.99V1-xPxO4:0.01Bi3+ (YV1-xPxO4:Bi3+) is used as the model; when the band gap of the activator Bi3+ increases from 3.44 to 3.76 eV and the band gap of the host YV1-xPxO4 widens from 2.75 to 3.16 eV, the electron-transfer potential energy (ΔET) decreases and the thermal quenching activation energy (ΔE) increases, which result in the relative emission intensity increasing from 0.06 to 0.64 at 303-523 K. Guided by density functional calculations, the thermal quenching mechanism of the Bi3+-MMCT state transition luminescence is revealed by the double-band-gap modulation model of the activator ion and the matrix. This study improves the thermal quenching theory of different types of Bi3+ transition luminescence and offers one neo-theory guidance for the contriving and researching of high-quality luminescence materials.

A solid-solution modulation strategy in trivalent bismuth-doped gallate phosphors for single substrate tunable emission.

The synthesis conditions of most phosphors doped with lanthanide ions with d-f transition require a reducing atmosphere. The doping Bi3+ ions selected in this study perfectly avoid this requirement, and they are environmentally friendly and safe. Nevertheless, the spectral tuning of Bi3+ is a great challenge that limits its application. Herein, by regulating the value of x in the new solid solution Sr2+xLa1-xGaO5-xFx, the luminescence of Bi3+ is well promoted. Through an excitation-driven strategy, the emission peak position of Bi3+ is redshifted, and the luminescence of trivalent bismuth is successfully adjusted, which can also be applied to anti-blue lighting. In addition, we constructed a Bi3+-Eu3+ dual luminescence system, and, regardless of changes in the Bi3+/Eu3+ concentration or excitation wavelength, a single matrix white light phosphor was realized. Through calculations, the activation energy of the phosphor doped with 2.5%Eu3+ was found to be 0.257 eV, which is higher than the activation energy of some common compounds. This indicates that the phosphor has good application prospects in the field of solid-state lighting. It is worth noting that based on the different thermal response behaviors of Bi3+ and Eu3+, when the Eu3+ content is fixed at 1%, the maximum relative sensitivity of the optical thermometer based on its fluorescence intensity ratio is about 1.46% K-1 at 383 K, which is higher than that of Bi3+ and Eu3+ co-doped phosphors previously reported. We also obtained a high absolute sensitivity of 0.00139 K-1 at 403 K. Therefore, we also studied the thermal sensitivity of Bi3+ and Er3+ co-doped solid solutions. The results show that this solid-solution phosphor has far-reaching application prospects in the temperature sensing field.

A colorimetric optical thermometry of host-sensitized Pr3+-doped niobate phosphors based on electronic-rich-site strategy.

Most praseodymium-doped red-emitting phosphors need high-temperature synthesis conditions with a reducing atmosphere. The niobate matrix selected in this work provides a sufficient electron-rich-site environment for praseodymium through charge migration, and praseodymium can be self-reduced in air atmosphere, which is safe and environmentally friendly. By building the [NbO6] group → Pr3+ energy transfer and finely modifying the doping concentration of Pr3+ ions, we constructed a dual-luminescence-system of the [NbO6] group and Pr3+. Thereby, optical temperature measurement based on fluorescence intensity ratio (FIR) technology of Pr3+ ions and [NbO6] groups was carried out using non-thermal coupling pairs, through the Boltzmann fitting and integral calculation, the maximum Sr and Sa values were 2.25% K-1 and 0.0049 K-1 at 403 K and 443 K, respectively, the Sr value is four times that obtained from the thermal coupling of Pr3+ ions, which exceeded most values previously reported for the fluorescence powder. Accordingly, we also studied the thermal sensitivity of Er3+ ions and Eu3+ ions mono-doped CaNb2O6 substrates. Results reveal that CaNb2O6:Pr3+/Er3+/Eu3+ phosphors have splendid temperature sensitivity and have far-reaching application prospects in the field of temperature measurements.

Photoluminescence and optical temperature measurement of Mn4+/Er3+ co-activated double perovskite phosphor through site-advantageous occupation.

Because traditional methods based on thermal coupling energy level temperature measurement have large errors, a new temperature sensing strategy is proposed to attain strong sensitivity and excellent signal resolution ability. The rare-earth and also transition metal ions with poles apart thermal quenching channels are used as dual emission centers to find a suitable host to achieve high-efficiency dual-mode emission. In this work, a string of phosphors with NaLaMgWO6 (NLMW) as the host, the single-doped and double-doped Mn4+ and Er3+ phosphors were adopted by the traditional high temperature solid-state reaction method. The crystallographic structure of the phosphor was analyzed by X-ray power diffraction and Rietveld refinement methods, and the results showed that a pure double perovskite phosphor with a monoclinic structure was successfully prepared. The photoluminescence excitation and emission spectrum properties, CIE chromaticity coordinates and photoluminescence spectra at different temperatures are detailed studied. Excited by ultraviolet light (300 nm), corresponding to the 4A2→4T1 transition of Mn4+ and the charge transfer from O2- to W6+ of Er3+. There is no energy transfer between Mn4+ and Er3+. NLMW:Mn4+/Er3+ phosphors were especially sensitive to temperature changes within the scope of 303 K to 523 K. As the temperature increases, the fluorescence intensity of Mn4+ is thermally quenched faster than Er3+. The luminescent intensity ratio of Er3+ thermal coupling level and the FIR of Er3+/Mn4+ are used to study the temperature performance. The results show that the maximum relative sensitivity of FIR up to 1.31% K-1, which is higher than the maximum temperature sensitivity based on the thermal coupling energy level, and which is beyond most of the non-contact temperature measurement materials previously reported, confirming that NLMW:Mn4+/Er3+ phosphors have application potential in non-contact temperature measurement.

NIR-triggered upconversion nanoparticles@thermo-sensitive liposome hybrid theranostic nanoplatform for controlled drug delivery.

Posterior segment ocular diseases are highly prevalent worldwide due to the lack of suitable noninvasive diagnostic and therapeutic tactics. Herein, concerning this predicament, we designed a hybrid retina-targeted photothermal theranostic nanoplatform (UCNPs@Bi@SiO2@GE HP-lips), based on the unique upconversion luminescence (UCL) imaging of upconversion nanoparticles (UCNPs), efficient photothermal conversion ability of Bi nanoparticles, and thermal-induced phase transition properties of the liposomes (lips). The nanoplatform was functionalized with penetratin (PNT) and hyaluronic acid (HA), to obtain retina-targeted liposomes (HP-lips). Lipophilic genistein (GE) was entrapped into the liposomes (GE HP-lips). An in vitro release study showed NIR irradiation could photothermally trigger controlled release of GE from the liposomal platform. Moreover, cellular uptake evaluation via UCL imaging demonstrated UCNPs@Bi@SiO2@GE HP-lips represented the brightest UCL, compared with other formulations, which is beneficial for the accurate evaluation of the prognosis and severity of angiogenesis-related posterior segment disorders. Therefore, UCNPs@Bi@SiO2@GE HP-lips exhibit promising potential as a theranostic nanoplatform for posterior segment ocular diseases.

Anisotropic Protein Organofibers Encoded With Extraordinary Mechanical Behavior for Cellular Mechanobiology Applications.

Hydrogels enable a variety of applications due to their dynamic networks, structural flexibility, and tailorable functionality. However, their mechanical performances are limited, specifically in the context of cellular mechanobiology. It is also difficult to fabricate robust gel networks with a long-term durability. Thus, a new generation of soft materials showing outstanding mechanical behavior for mechanobiology applications is highly desirable. We combined synthetic biology and supramolecular assembly to prepare elastin-like protein (ELP) organogel fibers with extraordinary mechanical properties. The mechanical performance and stability of the assembled anisotropic proteins are superior to other organo-/hydrogel systems. Bone-derived mesenchymal cells were introduced into the organofiber system for stem-cell lineage differentiation. This approach demonstrates the feasibility of mechanically strong and anisotropic organonetworks for mechanobiology applications and holds great potential for tissue-regeneration translations.

Engineered Anisotropic Fluids of Rare-Earth Nanomaterials.

The self-assembly of inorganic nanoparticles into well-ordered structures in the absence of solvents is generally hindered by van der Waals forces, leading to random aggregates between them. To address the problem, we functionalized rigid rare-earth (RE) nanoparticles with a layer of flexible polymers by electrostatic complexation. Consequently, an ordered and solvent-free liquid crystal (LC) state of RE nanoparticles was realized. The RE nanomaterials including nanospheres, nanorods, nanodiscs, microprisms, and nanowires all show a typical nematic LC phase with one-dimensional orientational order, while their microstructures strongly depend on the particles' shape and size. Interestingly, the solvent-free thermotropic LCs possess an extremely wide temperature range from -40 °C to 200 °C. The intrinsic ordering and fluidity endow anisotropic luminescence properties in the system of shearing-aligned RE LCs, offering potential applications in anisotropic optical micro-devices.

Biocompatible and pH-Responsive Colloidal Surfactants with Tunable Shape for Controlled Interfacial Curvature.

Molecular-surfactant-stabilized emulsions are susceptible to coalescence and Ostwald ripening. Amphiphilic particles, which have a much stronger anchoring strength at the interface, could effectively alleviate these problems to form stable Pickering emulsions. Herein, we describe a versatile method to fabricate biocompatible amphiphilic dimer particles through controlled coprecipitation and phase separation. The dimer particles consist of a hydrophobic PLA bulb and a hydrophilic shellac-PEG bulb, thus resembling nonionic molecular surfactants. The size and diameter ratio of the dimer particles are readily tunable, providing flexible control over the water/oil interfacial curvature and thus the type of emulsion. The particle-stabilized emulsions were stable for a long period of time and could be destabilized through a pH-triggered response. The biocompatible amphiphilic dimer particles with tunable morphology and functionality are thus ideal colloidal surfactants for various applications.

Enhancing Luminescence and Controlling the Mn Valence State of Gd3Ga5-x-δAlx-y+δO12:yMn Phosphors by the Design of the Garnet Structure.

Gd3Ga5-x-δAlx-y+δO12:yMn solid solutions with improving luminescence properties were prepared via cation substitution and a controllable Mn valence state. The abnormal autoreduction from Mn4+ to Mn2+ ions was observed during the formation of Gd3Ga5-x-δAlx-y+δO12:yMn. The doped manganese ions occupy octahedral Ga3+(1) and Al3+(1) sites to form the Mn2+ luminescent center with red emission at 630 nm and Mn4+ luminescent centers with deep red light emission at 698 nm, respectively, matching well with the red light absorption of phytochrome (PR) and the far-red light absorption of phytochrome (PFR). With the design of the concentration of Al3+ and doped manganese ions, the photoluminescence (PL) of Mn4+/Mn2+ (corresponding to PFR/PR) can be tuned, which is very useful for controlling the plant growth. Moreover, the PL intensity of Gd3Ga5-x-δAlx-y+δO12:yMn can be increased by 6.8 times by substituting Al3+ for Ga3+. The thermal stability is also enhanced significantly. Finally, a series of warm white-light-emitting diodes (WLEDs) with good performance were fabricated using the as-prepared Gd3Ga5-x-δAlx-0.012+δO12:0.012Mn phosphor. The results show that the designed Gd3Ga5-x-δAlx-y+δO12:yMn phosphors have potential practical values in plant-growth light-emitting diodes (LEDs) and high-performance WLEDs. Moreover, our strategy not only provides a unique inspiration for tuning the valence states of Mn but also designs new advanced luminescent materials.

One-pot synthesis of Ln3+-doped porous BiF3@PAA nanospheres for temperature sensing and pH-responsive drug delivery guided by CT imaging.

The design and synthesis of responsive inorganic nanocapsules have attracted intensive research interest in cancer treatment. The combination of non-invasive diagnosis and chemotherapy into a single theranostic nanoplatform is prospective in the biomedical field. In this work, a polyacrylic acid (PAA)-functionalized porous BiF3:Yb,Er nanocarrier was constructed via a straightforward one-pot solvothermal strategy. Compared with the undoped BiF3 sub-microspheres, the lanthanide ion (Ln3+) doping endowed the BiF3 material with a smaller size and increased BET specific surface area and pore volume, which make it suitable as a drug carrier. It was found that the synthesized nanomaterial could effectively relieve the side effects of doxorubicin (DOX) and exhibited pH-dependent DOX loading and release. Its satisfactory biocompatibility and efficient tumor inhibition were emphasized by a series of in vitro/in vivo experiments. In addition, the synthesized nanomaterial exhibited favorable CT contrast efficacy due to the excellent X-ray attenuation coefficient of Bi. Moreover, characteristic upconversion luminescence and temperature sensing in a wide temperature range were realized over the synthesized BiF3:Yb,Er sample. Therefore, carboxyl-functionalized BiF3:Yb,Er can be expected to be an ideal candidate in the fabrication of temperature sensing and multifunctional theranostic nanoplatforms.

UCNP-Bi2 Se3 Upconverting Nanohybrid for Upconversion Luminescence and CT Imaging and Photothermal Therapy.

Non-invasive theranostics that integrate the advantages of multimodality imaging and therapeutics have great potential in the field of biomedicine. Herein, a new nanohybrid based on Bi2 Se3 -conjugated upconversion nanoparticles (UCNPs) has been successfully developed through a simple in situ growth strategy. Under 808 nm near-infrared laser irradiation, the UCNPs can emit bright visible light, whereas the Bi2 Se3 nanomaterial exhibits efficient photothermal conversion capacity. Moreover, the as-synthesized UCNP-Bi2 Se3 nanohybrid exhibits efficient cell upconversion luminescence (UCL), reasonable CT imaging, and admirable cancer cell ablation capacity, further emphasizing the efficiency of this strategy for simultaneous UCL imaging and photothermal therapy. The designed theranostic strategy guided by dual-modal imaging endowed with real-time dynamic monitoring, remote controllability, and non-invasiveness makes the UCNP-Bi2 Se3 nanohybrid an ideal candidate for non-invasive multimodal imaging-guided photothermal therapy for the precise diagnosis and treatment of cancer.

Novel NIR LaGaO3:Cr3+,Ln3+ (Ln = Yb, Nd, Er) phosphors via energy transfer for C-Si-based solar cells.

A series of Cr3+-Yb3+/Nd3+/Er3+ codoped LaGaO3 phosphors were synthesized by a traditional solid-state method. The morphology, crystal structure, phase purity, and the luminescence properties of samples were characterized by using X-ray diffraction, Rietveld refinement, field-emission scanning electron microscopy, and photoluminescence. The obtained phosphors exhibit efficient broad absorption in the near ultraviolet and visible (UV-Vis) region and intense near infrared (NIR) emission, due to the energy transfer process from the Cr3+ to Yb3+/Nd3+/Er3+ ions, which match well with the maximum photon flux region of the solar spectrum and the optimal spectral response of the C-Si solar cell. Moreover, we also observed an energy transfer from the Nd3+/Er3+ to Yb3+ ions. The efficiency was investigated and analyzed by the visible and NIR emission spectra and lifetime decay curve and the energy transfer efficiency was as high as 77%. Our results reveal that the Cr3+-Yb3+/Nd3+/Er3+ codoped phosphors are promising materials for enhancing the efficiency of solar cells.

Preparation and photoluminescence of novel La8Ca2(Si4P2O22N2)O2 oxynitride phosphors containing Eu2+/Ce3+/Tb3+ ions.

A series of novel Eu2+/Ce3+/Tb3+ ion doped La8Ca2(Si4P2O22N2)O2-based apatite structure oxynitride phosphors have been synthesized by a solid-state method. The phase purity has been checked by X-ray diffraction (XRD) and the Rietveld method. The photoluminescence excitation (PLE) spectra indicate that the obtained phosphors have broad excitation bands in the n-UV range, which is a favourable property for application as n-UV-WLED phosphors. The concentration quenching has been investigated in detail. The temperature-dependent luminescence and efficiency study shows that the as-prepared phosphors have a good thermal stability and high quantum efficiency. Moreover, a warm white LED device with a low color temperature of 4288 K and a high color rendering index (Ra) of 80.8 has been obtained by coating a La8Ca1.99(Si4P2O22N2)O2:0.01Eu2+ phosphor with a (Sr,Ca)AlSiN3:Eu2+ red phosphor on a n-UV chip. Our results reveal that the La8Ca2(Si4P2O22N2)O2:Eu2+ phosphor is a promising bluish-green phosphor for WLEDs.

Designing of UCNPs@Bi@SiO2 Hybrid Theranostic Nanoplatforms for Simultaneous Multimodal Imaging and Photothermal Therapy.

Herein, a novel multifunctional nanoplatform was designed toward multimodality imaging and photothermal therapy (PTT). It was found that Bi nanoparticles could grow in situ on the surface of NaYF4:20%Yb,2%Er@NaYF4:40%Yb@NaGdF4 core-shell nanoparticles (labeled as UCNPs). In this structure, UCNPs were mainly employed as an upconversion luminescence (UCL) imaging agent, whereas the Bi nanoparticles worked as an effective CT imaging and photothermal agent. Importantly, a dense SiO2 shell was employed to protect the Bi nanoparticles from oxidation, and it also endowed the nanoplatform with excellent hydrophilic ability. The effective UCL/CT imaging and PTT performances were emphasized by a series of in vivo experiments, which suggest that the integrated nanoplatform with imaging and therapy functions shows great promise in the biomedical field.

Renal-Clearable Peptide-Functionalized Ba2GdF7 Nanoparticles for Positive Tumor-Targeting Dual-Mode Bioimaging.

Considering the dilemma between the effective tumor targeting and the avoidance of potential toxicity, it is desired to design nanoprobes with positive tumor-targeting and good renal clearance ability. In the present work, we developed epidermal growth factor receptor (EGFR)-targeted peptide-functionalized Ba2GdF7 nanoparticles (termed as pEGFR-targeted Ba2GdF7 NPs) for positive tumor-targeting magnetic resonance imaging and X-ray computed tomography (MRI/CT) dual-mode bioimaging. The positive tumor-targeting ability of pEGFR-targeted Ba2GdF7 NPs is achieved by conjugation of EGFR-targeted peptides on the 6.5 nm Ba2GdF7 NP surface through the formation of Gd-phosphonate coordinate bonds. The pEGFR-targeted Ba2GdF7 NPs display desirable cytocompatibility in the test concentration range and high binding affinity with lung cancer cells. In vivo MR and CT imaging results demonstrate that the pEGFR-targeted Ba2GdF7 NPs are able to be accumulated and detained within an engrafted A549 lung carcinoma, which enhances both MR and CT contrast in the tumor tissue. Systematic in vivo experimental results further demonstrate that the pEGFR-targeted Ba2GdF7 NPs have favorable in vivo renal clearance kinetics as well as reasonable in vivo biocompatibility.

Genetically Engineered Supercharged Polypeptide Fluids: Fast and Persistent Self-Ordering Induced by Touch.

Mechanically induced disorder-order transitions have been studied in fluid surfactant solutions or polymer thermotropic liquid crystals. However, isothermally induced ordered phases do not persist after cessation of shear, which limits their technological applicability. Moreover, no such stimuli-responsive materials involving biomacromolecules have been reported although biopolymer liquids are gaining a lot of attention. A biological fluid system is introduced in which anionic polypeptides are complexed with cationic surfactants. The resulting fluids exhibited very sensitive isotropic-nematic transition triggered by shear. The formed liquid crystal was preserved after cessation of mechanical stimulus. Self-ordering behavior of the material was achieved through water flow and finger pressing. The latter mechanical induction resulted in the formation of complex pattern that can be read out by birefringence, allowing the recording of fingerprint information.

Facile Synthesis of Lanthanide (Ce, Eu, Tb, Ce/Tb, Yb/Er, Yb/Ho, and Yb/Tm)-Doped LnF3 and LnOF Porous Sub-Microspheres with Multicolor Emissions.

Monodisperse YF3 and YOF porous sub-microspheres were synthesized by using a novel sacrificing template method with amorphous Y(OH)CO3 ⋅x H2 O as the precursors and the template. It was found that the size and shape were well maintained, and the condensed precursor was transformed into uniform porous structures after fluoridation. By fine-tuning the feed of the fluorine source, the final product could be converted from YF3 to YOF. A possible growth mechanism is proposed for the uniform porous YF3 structure and the porous yolk-shell-like YOF structure. The luminescence properties showed that the as-synthesized YF3 :Ln3+ (Ln=Eu, Tb, Ce, Ce/Tb, Yb/Er, Yb/Ho, and Yb/Tm) products exhibited strong multicolor emissions, which included down-/upconversion and energy-transfer processes. Additionally, YOX (X=Cl and Br) could be obtained if a different halogen source was used during calcination. However, the spheres were almost completely destroyed. Our novel synthetic route can also be extended to other lanthanide fluorides (REF3 , RE=Gd, Lu), which may open a facile way to fabricate novel porous nanostructures.