K2LiScF6:Cr3+/Mn4+ fluoride phosphor with enhanced broadband emission for NIR pc-LEDs.

Trivalent chromium ion-activated broadband near-infrared (NIR) luminescence materials have shown great application prospects as next-generation NIR light sources, but improvement of the luminescence efficiency remains a challenge. Herein, novel K2LiScF6:Cr3+ and K2LiScF6:Cr3+/Mn4+ broadband fluoride NIR phosphors are designed and prepared by a combination of hydrothermal and cation exchange methods for the first time. The crystal structure and photoluminescence (PL) properties of K2LiScF6:Cr3+ are studied in detail, which shows strong absorption in the blue light region (λex = 432 nm) and broadband NIR emission (λem = 770 nm) with a PL quantum efficiency of 77.6%. More importantly, the NIR emission of Cr3+ can be enhanced by co-doping with Mn4+, which may provide an alternative way for improving the PL intensity of Cr3+-activated broadband NIR phosphors. Finally, a NIR phosphor-converted LED (pc-LED) device is fabricated using the as-prepared NIR phosphor and its application in bio-imaging and night vision has been evaluated.

Boosting Red Luminescence of Mn4+ in Tantalum Heptafluoride Based on an Ab Initio-Facilitated Sensitizer and Hydrophobic Surface Modification.

A narrow-band red-light component is critical to establish high color rendition and a wide color gamut of phosphor-converted white-light-emitting diodes (pc-WLEDs). In this sense, Mn4+-doped K2SiF6 fluoride is the most successful material that has been commercialized. As with K2SiF6:Mn4+ phosphors, Mn4+-doped tantalum heptafluoride (K2TaF7:Mn4+) fulfills a similar luminescence behavior and has been brought in a promising narrow-band red phosphor. But the limited brightness and low moisture-resistant performances have inevitably blocked its practical application. Herein, we employed the density functional theory (DFT)-based ab initio estimation approach to quickly identify the proper sensitizer by systematically investigating the electronic-band coupling between the several possible sensitizers (Rb, Hf, Zr, Sn, Nb, and Mo) and the luminescent center (Mn). Combined with experimental results, Mo was demonstrated to be the optimal sensitizer, which resulted in a 60% enhancement of the emission. On the side, the moisture sensitivity has been effectively improved via grafting the hydrophobic octadecyltrimethoxysilane (ODTMS) layer on the phosphor surface. Through employing the K2TaF7:Mn4+,Mo6+@ODTMS composite as a red component, warm WLEDs with good performance were achieved with a correlated color temperature (CCT) of 4352 K, a luminous efficacy (LE) of 90.1 lm/W, and a color rendering index (Ra) of 83.4. In addition, a wide color gamut reaching up to 102.8% of the NTSC 1953 value could be realized. Aging tests at 85 °C and 85% humidity for 120 h on this device manifested that the ODTMS-modified phosphor had much better moisture stability than that of the unmodified one. These studies provided viable tools for optimizing Mn4+ luminescence in fluoride hosts.

Enlarging Sensitivity of Fluorescence Intensity Ratio-Type Thermometers by the Interruption of the Energy Transfer from a Sensitizer to an Activator.

The occurrence of energy transfer (ET) would enhance the luminescence of the activator but sacrifice that of the sensitizer. However, the novel Sm3+-doped Ca2TbSn2Al3O12 (CTSAO) phosphor reported here seems to be an exception. In the series of CTSAO:xSm3+ phosphors investigated, something unexpected occurs; the activator, Sm3+, did not gain any energy compensation from the sensitizer, Tb3+, when temperature increases. Instead, when the loss of Sm3+ luminescence accelerates, simultaneously, the loss of Tb3+ luminescence accordingly alleviates. By careful calculations on the ET efficiency of the CTSAO:0.06Sm3+ phosphor at different temperatures, it is surprisingly found that the efficiency keeps decreasing as temperature increases. It means that the Tb3+-Sm3+ energy transfer is capable of being interrupted by an increasing temperature. By simulation, it is found that the occurrence of thermal interruption of energy transfer benefits the achievement of a higher temperature sensing sensitivity. In this sense, making use of the thermal interruption of energy transfer could become a novel route for further design of the fluorescence intensity ratio-type luminescence thermometers.

Key Role Effect of Samarium in Realizing Zero Thermal Quenching and Achieving a Moisture-Resistant Reddish-Orange Emission in Ba3LaNb3O12:Sm3.

The strategy to enhance phosphor stability against thermal quenching and moisture conditions will contribute to controlling the feature of phosphor-converted white-light-emitting diodes (pc-WLEDs). Herein, an effective strategy is achieved with the incorporation of Sm3+ ions, and a robust reddish-orange emission (no thermal quenching up to 498 K) is obtained based on Ba3LaNb3O12 as a host. In light of excitation by near-ultraviolet irradiation at 408 nm, Ba3LaNb3O12:Sm3+ gives rise to a typical signal ascribed to the 4G5/2 → 6HJ/2 (J = 5, 7, 9, and 11) transitions of Sm3+ ions. The concentration quenching effect is observed when the Sm3+ content exceeds 10%, and the quenching mechanism is caused by electronic dipole-dipole interactions. Based on the narrow emission curves, a very high color purity (92.4%) could be recorded. The Sm3+ substitution at the Ba2+/La3+ site leads to a rigid structural lattice and abundant electron-trapping centers for the Sm3+ ions, which will be responsible for the zero-thermal-quenching phenomenon. In addition, oleic acid (OA) is selected to form a hydrophobic covering surface structure to protect Ba3LaNb3O12:Sm3+, which can assist in improving the moisture resistance. The most favorable parameters concerning the warm-light emission (a high general color rendering index, Ra, of 85.7 and a low correlated color temperature, CCT, of 4965 K) can be achieved in pc-WLEDs containing an OA-modified sample. Moreover, its luminous efficiency, LE, can maintain 82.9% of its initial value after 120 h under controlled environmental conditions of 85 °C and 85% humidity. These results pave a new way to optimize the sample as a potential candidate for red-emitting materials.

Crystal-field induced tuning of luminescence properties of Na3GaxAl1-xF6:Cr3+ phosphors with good thermal stability for NIR LEDs.

Cr3+-Activated broadband near-infrared (NIR) luminescence materials are attracting much attention as next-generation smart NIR light sources that are widely used in night vision, bioimaging, medical treatment, and many other fields. Herein, a series of Na3GaxAl1-xF6:Cr3+ NIR phosphors with broadband emission and tunable luminescence properties were designed and prepared. The luminescence intensity, peak position and full width at half maximum (FWHM) of the materials can be controlled by adjusting the crystal field strength. Furthermore, Na3Ga0.75Al0.25F6:0.35Cr3+ exhibited high luminous efficiency and the emission intensity remained 81% at 423 K compared with the initial value at 298 K. The structural confinement and the electron-phonon coupling (EPC) effect may account for its good thermal stability. Finally, a pc-NIR-LED device with a photoelectric conversion efficiency of 6.53% at 350 mA was fabricated by combining the as-prepared NIR phosphor and a blue InGaN chip, and its applications in night vision and medical fields were further investigated. This work will promote the development of NIR phosphors with tunable luminescence properties.

Sensitization of Mn2+ luminescence via efficient energy transfer to suit the application of high color rendering WLEDs.

Developing novel luminescent materials with ideal properties is an endless project, urged by growing requirements of advances in energy saving, healthy lighting and environmental friendliness. Herein, a series of ScCaOBO3:Ce3+,Mn2+ phosphors with excellent luminescence properties were synthesized by the high temperature solid state method. X-ray diffraction was applied to analyse the phase composition of the obtained phosphors. The morphology and dopant distribution were observed by scanning electron microscopy (SEM) and energy dispersive spectrometry (EDS), respectively. The Rietveld refinements and luminescence spectra indicate that Ce3+ preferentially occupies the Sc3+ site and produces a blue emission band at around 460 nm, which originates from the characteristic 5d-4f transitions, while Mn2+ preferentially occupies the Ca2+ site and emits red light due to its characteristic 4T1(4G)-6A1(6S) transitions. Upon excitation at 354 nm, both Ce3+ and Mn2+ emissions can be obtained and further investigations evidenced that the broad and intense light emission of Mn2+ located in the red spectral region is the result of energy transfer from Ce3+ to Mn2+. Theoretical calculations reveal that the energy transfer process from Ce3+ to Mn2+ is of the resonance type and is governed by electric dipole-dipole interactions. Since the ScCaOBO3:Ce3+,Mn2+ phosphors are capable of producing broadband emissions that widely cover the blue and red spectral regions, the introduction of a green light-emitting phosphor CMA:Tb3+ can conveniently generate high quality white light. Therefore, a white light-emitting diode device with extremely high color rendering indices, Ra = 93.7 and R9 = 91.9, was successfully obtained.

Realization of an Optical Thermometer via Structural Confinement and Energy Transfer.

The influence of temperature on a variety of physiological or chemical processes has generated considerable interest, and recently noninvasive lanthanide-incorporated optical thermometers have been considered as promising candidates for monitoring its changes at different scales. Herein, a novel Bi3+-activated Sr3-xGdxGaO4+xF1-x phosphor with tunable color has been constructed by a cooperative cation-anion substitution strategy with to the replacement of [Sr2+-F-] by [Gd3+-O2-]. When x = 0, the sample Sr3GaO4F/Bi3+ possesses a peak wavelength at 438 nm, and this value will shift to 470 nm if x is equal to 1 (Sr2GdGaO5/Bi3+). In addition, photoluminescence tuning from blue to red has been realized successfully by an efficient Bi3+ → Eu3+ energy migration model in Sr2.6Gd0.4GaO4.4F0.6 samples. The specific Bi3+ → Eu3+ energy transfer has been explained by dipole-dipole interactions derived from a model of the Dexter pathway. Intriguingly, the two dopants (a blue signal from Bi3+ and a red signal from Eu3+) possess different thermal responses to increasing temperature. Accordingly, the intensity ratio values are sensitive to the temperature changes. The energy level cross relaxation causes the quenching effect of Bi3+, and the multi-phonon de-excitation mode leads to the thermal quenching of Eu3+. At room temperature (298 K), the determined maximum relative sensitivity (Sr) is 1.27% K-1. Moreover, the absolute sensitivity (Sa) is 0.067 K-1 since the temperature is elevated to 523 K. The collected results are superior to most of the reported optical thermometry materials.

Extension of Spectral Shift Controls from Equivalent Substitution to an Energy Migration Model Based on Eu2+/Tb3+-Activated Ba4-xSrxGd3-xLuxNa3(PO4)6F2 Phosphors.

Single-phase phosphors with tunable emission colors are crucial to develop high-performance white light-emitting diodes since they are valuable to improve the energy efficiency, color rendering index, and correlated color temperature. Most of the studies have been conducted to control the spectral shifts via a polyhedral distortion or chemical unit cosubstitution strategy. The combination of host optimization and dopant activator design in a single-phase phosphor system is very rare. Herein, a partial substitution strategy of [Ba2+-Gd3+] by [Sr2+-Lu3+] has been employed in Ba4-xSrxGd3-x-yLuxNa3(PO4)6F2/5% Eu2+ (x = 0-0.40) phosphors. Also, the energy migration from Eu2+ to Tb3+ ions has been investigated in as-prepared samples. Consequently, the emitted signal is observed to shift from 470 to 575 nm derived from equivalent substitutions, which is attributed to specific performance by the emission profile of Eu2+, and such results are closely related to splitting of the crystal field and energy transfer among various luminescent centers. Moreover, the tunable yellowish-green emitting material has been assembled by incorporating ion pairs (Eu2+ → Tb3+) into the Ba3.85Sr0.15Gd2.85Lu0.15Na3(PO4)6F2, and their relative ratios are varied. The corresponding Eu2+ → Tb3+ energy migration process is assigned to be the dipole-quadrupole interaction by the Inokuti-Hirayama model. This work provides rational guidance for the design and discovery of new products with tunable emission colors, originating from the cosubstitution strategy and energy conversion model.

Efficient Energy Transfer from Trap Levels to Eu3+ Leads to Antithermal Quenching Effect in High-Power White Light-Emitting Diodes.

The most critical aspect in the assembly of phosphor-converted white light-emitting diodes (pc-WLEDs) is how to stabilize the device in a practical environment. The high applied currents can generate enormous heat up to more than 100 °C, and such a continuous illumination process will lead to serious effects concerning the stability of the device. Therefore, the new search for examples to fully suppress thermal quenching effect is a real challenge. In this study, a novel Eu3+-activated CaMgGeO4 (CMGO) phosphor of olivine type is developed via a conventional solid-state reaction. The results reveal that Eu3+ occupies the low symmetric Ca2+ site of this host. Upon visible-light sensitization at 464 nm, a dominant red emission band with maximum at 612 nm is witnessed. Its full width at half-maximum (fwhm) is merely ∼4.37 nm, and a high color purity of around 94% is achieved. Their corresponding Commission Internationale de L'Eclairage (CIE) coordinates are very close to standard red color coordinates (0.666, 0.333). The influence of concentration and temperature on the optical property has been explored. It has been discovered that the optimized sample (CMGO:0.01Eu3+) is not influenced by the thermal quenching effect and its fluorescent intensity is improved even up to 473 K, which is mainly attributed to the incorporation of abundant trap sites generated by the nonequivalent substitution Eu3+ for Ca2+. After it is integrated into commercially available YAG:Ce3+ phosphor-based pc-WLEDs, the excellent optical parameters of the fabricated WLEDs are evaluated. The correlated color temperature (CCT) varies from cool white (6458 K) to warm (4370 K), and the color rendering index (CRI) increases from 78 to 86 under a high flux operating current of 200 mA. Furthermore, the chromaticity coordinates remain almost stable with the increasing drive current from 200 mA to 1000 mA. It is highly expected that CaMgGeO4:0.01Eu3+ will become a suitable red phosphor for the preparation of white LEDs with high efficiency.

A New Co-Substitution Strategy as a Model to Study a Rare-Earth-Free Spinel-Type Phosphor with Red Emissions and Its Application in Light-Emitting Diodes.

The substitution of metal sites in Mg2TiO4 substrate leads to charge imbalance that will be closely related to a variety of changes including lattice structure, cell distortion, and photophysical properties. Herein, the co-substitution strategy of [Ga3+-Ga3+] for [Mg2+-Ti4+] and Sn4+ for Ti4+ achieves for the first time the novel Mg3Ga2SnO8 (MGS):xMn4+ (x = 0-3%) phosphors with efficient red emissions. In terms of X-ray powder diffraction (XRD) and Rietveld refinement analysis, MGS:Mn4+ possesses a structure isotypic of Mg2TiO4 in the cubic space group Fd3̅m (227). There are two types of octahedra for Mn4+ ions in this structure, where Ga3+ ions completely occupy a group of octahedral sites and Mg2+/Sn4+ has been randomly distributed over another group of octahedral sites. A strong excitation band in the broad spectral range (220-550 nm) has been identified, thus facilitating the commercial uses for blue LED chips excitation. An intense red emission band at 680 nm has been observed due to the characteristic 2Eg-4A2g transition of Mn4+ ions. A concentration quenching effect occurs when the Mn4+ content exceeds 1.5%, and the quenching mechanism is demonstrated to be dipole-quadrupole interactions. Temperature-dependent luminescence measurements support its good thermal stability, and the corresponding activation energy Ea is determined to be 0.2552 eV. The possible luminous mechanism of the Mn4+ ion is explained by the Tanabe-Sugano energy level diagram. The crystal field strength and the Racah parameters together with the nephelauxetic ratio are also determined for Mn4+ in the MGS lattice. High color rendition warm white-light-emitting diodes (WLEDs) based on the optimal phosphor MGS:1.5%Mn4+,1.5%Li+ possess a color rendering index and color temperature of 85.6 and 3658 K, respectively. Its feasibility for application in solid-state white lighting has been verified.

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.

Tunable white light of a Ce3+,Tb3+,Mn2+ triply doped Na2Ca3Si2O8 phosphor for high colour-rendering white LED applications: tunable luminescence and energy transfer.

A tunable white light emitting Na2Ca3Si2O8:Ce3+,Tb3+,Mn2+ phosphor with a high color rendering index (CRI) has been prepared. Under UV excitation, Na2Ca3Si2O8:Ce3+ phosphors present blue luminescence and exhibit a broad excitation ranging from 250 to 400 nm. When codoping Tb3+/Mn2+ ions into Na2Ca3Si2O8, energy transfer from Ce3+ to Tb3+ and Ce3+ to Mn2+ ions is observed from the spectral overlap between Ce3+ emission and Tb3+/Mn2+ excitation spectra. The energy-transfer efficiencies and corresponding mechanisms are discussed in detail. The mechanism of energy transfer from Ce3+ to Tb3+ is demonstrated to be a dipole-quadrupole mechanism by the Inokuti-Hirayama model. The wavelength-tunable white light can be realized by coupling the emission bands centered at 440, 550 and 590 nm ascribed to the contribution from Ce3+, Tb3+ and Mn2+, respectively. The commission on illumination value of color tunable emission can be tuned by controlling the content of Ce3+, Tb3+ and Mn2+. Temperature-dependent luminescence spectra proved the good thermal stability of the as-prepared phosphor. White LEDs with CRI = 93.5 are finally fabricated using a 365 nm UV chip and the as-prepared Na2Ca3Si2O8:Ce3+,Tb3+,Mn2+ phosphor. All the results suggest that Na2Ca3Si2O8:Ce3+,Tb3+,Mn2+ can act as potential color-tunable and single-phase white emission phosphors for possible applications in UV based white LEDs.

Novel tunable green-red-emitting oxynitride phosphors co-activated with Ce3+, Tb3+, and Eu3+: photoluminescence and energy transfer.

A series of novel Ce3+, Tb3+ and Eu3+ ion doped Y4SiAlO8N-based oxynitride phosphors were synthesized by the solid-state method and characterized by X-ray powder diffraction, scanning electron microscopy, photoluminescence, lifetimes and thermo-luminescence. The excitation of the Ce3+/Tb3+ co-doped and Ce3+/Tb3+/Eu3+ tri-doped phosphor with near-UV radiation results in strong linear Tb3+ green and Eu3+ red emission. The occurrence of Ce3+-Tb3+ and Ce3+-Tb3+-Eu3+ energy transfer processes is responsible for the bright green or red luminescence. The Tb3+ ion acting as an energy transfer bridge can alleviate MMCT quenching between the Ce3+-Eu3+ ion pairs. The lifetime measurements demonstrated that the energy-transfer mechanisms of Ce3+→ Tb3+ and Tb3+→ Eu3+ are dipole-quadrupole and quadrupole-quadrupole interactions, respectively. The temperature dependent luminescence measurements showed that as-prepared green/red phosphors have good thermal stability against temperature quenching. The obtained results indicate that these phosphors might serve as promising candidates for n-UV LEDs.

Phase-Tunable Synthesis of Monodisperse YPO4:Ln3+ (Ln = Ce, Eu, Tb) Micro/Nanocrystals via Topotactic Transformation Route with Multicolor Luminescence Properties.

A novel aqueous-based and phase-selected synthetic strategy toward YPO4:Ln3+ (Ln = Ce, Eu, Tb) micro/nanocrystals was developed by selecting specific precursors whose structure topotactically matches with the target ones. It was found that layered yttrium hydroxide (LYH) induced the formation of hexagonal-phased h-YPO4·0.8H2O with the crystalline relationship of [001]LYH//[0001]h-YPO4·0.8H2O, while the amorphous Y(OH)CO3 favored the formation of tetragonal-phased t-YPO4. We also systematically investigated the influence of Na2CO3/NaH2PO4 feeding ratio on the evolutions of morphology and size of the h-YPO4·0.8H2O sample, and we also obtained a novel mesoporous nanostructure for t-YPO4 single crystalline with closed octahedron shape for the first time. Besides, the multicolor and phase-dependent luminescence properties of the as-obtained h-YPO4·0.8H2O and t-YPO4 micro/nanocrystals were also investigated in detail. Our work may provide some new guidance in synthesis of nanocrystals with target phase structure by rational selection of precursor with topotactic structural matching.

Emission Enhancement and Color Tuning for GdVO4:Ln3+ (Ln = Dy, Eu) by Surface Modification at Single Wavelength Excitation.

The surface modification can realize systematically the emission enhancement of GdVO4:Ln3+ (Ln = Dy, Eu) microstructures and multicolor emission at single component. The structure, morphology, composition, and the surface ligands modification of as-prepared samples were studied in detail. It is found that the surface-modified ligands can act as sensitizer to improve the emission of the Eu3+ and Dy3+ ions via the energy transfer besides the VO43--Eu3+/Dy3+ process. More importantly, under a single wavelength excitation, the emission color can be effectively tuned by manipulating the doping ratio of the Eu3+ ions in the internal crystal lattice and the Tb3+ ions in the external surface ligands, simultaneously. And further, multicolor emissions are obtained under single wavelength excitation due to the high overlapping between the VO43- absorption and the π-π* electron transition of the ligands. These findings may open new avenues to design and develop new highly efficient luminescent materials.

Efficient Chemical Synthesis of Functional Rare Earth Orthoborates Nanosheets and Their Photoluminescence Studies.

In contrast to routine methods, La x Y1−x BO3:Eu3+ and La y Lu1−y BO3:Eu3+ were efficiently prepared by a supersonic microwave co-assistance method within 60 minutes at 90 °C. Orderly aggregated nanosheets were formed in high yields by preferential crystal growth processes. More importantly, it has never been reported that the magnetic-dipole transition with orange-color emissions (5D0 → 7F1) could be finely tuned based on the concentration variation of lanthanum elements. The electronic dipole transition (5D0 → 7F2) increases gradually when La/Y and La/Lu ratios are 4/1 and 7/3 respectively.

Photoluminescence, energy transfer and tunable color of Ce(3+), Tb(3+) and Eu(2+) activated oxynitride phosphors with high brightness.

New tuneable light-emitting Ca3Al8Si4O17N4:Ce(3+)/Tb(3+)/Eu(2+) oxynitride phosphors with high brightness have been prepared. When doped with trivalent cerium or divalent europium they present blue luminescence under UV excitation. The energy transfer from Ce(3+) to Tb(3+) and Ce(3+) to Eu(2+) ions is deduced from the spectral overlap between Ce(3+) emission and Tb(3+)/Eu(2+) excitation spectra. The energy-transfer efficiencies and corresponding mechanisms are discussed in detail, and the mechanisms of energy transfer from the Ce(3+) to Tb(3+) and Ce(3+) to Eu(2+) ions are demonstrated to be a dipole-quadrupole and dipole-dipole mechanism, respectively, by the Inokuti-Hirayama model. The International Commission on Illumination value of color tuneable emission as well as luminescence quantum yield (23.8-80.6%) can be tuned by controlling the content of Ce(3+), Tb(3+) and Eu(2+). All results suggest that they are suitable for UV light-emitting diode excitation.

Synthesis and Luminescence Properties of LnM(v)O4 (M = Nb, Ta):RE3+ (RE = Eu, Tb) Nanophosphors.

A group of LnM(v)O4 (M = Nb, Ta):RE3+ (RE = Eu3+, Tb3+) phosphors have been synthesized by pretreatments with a special reactor (supersonic microwave co-assistance (SMC) machine). Powder characteristics were studied by X-ray Diffraction, photoluminescence, fluorescence microscope and scanning electronic microscope. Results showed the samples can exhibit green or red emissions upon the ultra-violet excitations. The influence of SMC method on the physical properties has been investigated in detail.