Red,green and blue-violet emission coexistence in white-light-emitting Ca3SiO4Cl2:Bi3+, Li+, Eu2+, Eu3+ phosphor

A series of emission-tunable Ca₃SiO₄Cl₂:Bi³⁺, Li⁺, Euⁿ⁺(n =2, 3) (CSC:Bi³⁺, Li⁺, Euⁿ⁺) phosphors have been synthesized via sol-gel method. The X-ray diffraction results indicate that the as-synthesized phosphors crystallize in a low temperature phase with the space group of P21/c. Energy transfer from Bi³⁺ to Eu³⁺/Eu²⁺ exists in CSC:Bi³⁺, Li⁺, Euⁿ⁺ phosphors. Under the excitation of 327 or 365 nm, the Ca_2.98−ySiO₄Cl₂:0.01Bi³⁺, 0.01Li⁺, yEuⁿ⁺(y=0.0001–0.002) phosphors show an intense green emission band around 505 nm, while under the excitation of 264 nm, three emission bands centered around 396 nm (Bi³⁺), 505 nm (Eu²⁺) and 614 nm (Eu³⁺) are observed and tunable colors from blue-violet to green or white are achieved in these phosphors by varying the content of Eu. White-light emission with the color coordinate (0.312, 0.328) is obtained in Ca_2.978SiO₄Cl₂:0.01Bi³⁺, 0.01Li⁺, 0.002Euⁿ⁺(n =2, 3). Based on these results, the as-prepared CSC:Bi³⁺, Li⁺, Eu²⁺, Eu³⁺ phosphors can act as color-tunable and single-phase white emission phosphors for potential applications in UV-excited white LEDs.     

Enhanced luminescence properties of Li2MgTiO4: Mn4+, Ge4+ phosphor via single cation substitution for indoor plant cultivation

Red and far-red emitting phosphors have been widely used in phosphor-converted light emitting diode (pc-LED) devices to provide lighting for indoor plant growth, thus achieving desired product qualities. Among the many ways to optimize phosphors’ optical performance, cationic substitution is one of the most effective methods. In this study, red phosphors (Li₂MgTi_1-x-yO₄: xMn⁴⁺, yGe⁴⁺) were synthesized by high temperature solid state method and the optical performance of phosphors were improved with increasing Ge⁴⁺ constituents. In particular, luminescence intensity of Li₂MgTiO₄: 0.002Mn⁴⁺, 0.1Ge⁴⁺ increased by 152% under 468 nm excitation, and the thermostability of emission intensity increases from 22% (y = 0) to 43% (y = 0.1), which is about twice as much. Finally, pc-LED device was fabricated via the red phosphor Li₂MgTiO₄: 0.002Mn⁴⁺,0.1Ge⁴⁺ coated on a 470 nm ultraviolet chip. By changing the proportion of the phosphor, the electroluminescence spectra of pc-LED device could match well with the absorption regions of plant pigments. Therefore, Li₂MgTiO₄: 0.002Mn⁴⁺, 0.1Ge⁴⁺ phosphor has potential application in plant lighting. Furthermore, this work can offer some helpful references for improving luminescent efficiency by simply modulating the chemical composition.     

Mn4+-related photoemission enhancement via energy transfer in La2MgGeO6:Dy3+, Mn4+ phosphor for plant growth light-emitting diodes

A double perovskite-type substrate of La₂MgGeO₆ (LMGO) was successfully synthesized via a high-temperature solid-state reaction method and was codoped with Mn⁴⁺ and Dy³⁺ to form a new deep-red phosphor (LMGO:Mn⁴⁺,Dy³⁺) for artificial plant growth light-emitting diodes (LEDs). This extraordinary phosphor can exhibit strong far-red emission with a maximum peak at 708 nm between 650 and 750 nm, which can be ascribed to the ²E_g → ²A_2 g spin-forbidden transition of Mn⁴⁺. The X-ray diffraction (XRD) patterns and high-resolution transmission electron microscopy (HRTEM) clarified that the La³⁺ sites in the host were partly replaced by Dy³⁺ ions. Moreover, we discovered energy transfers from Dy³⁺ to Mn⁴⁺ by directly observing the significant overlap of the excitation spectrum of Mn⁴⁺ and the emission spectrum of Dy³⁺ as well as the systematic relative decline and growth of the emission bands of Dy³⁺ and Mn⁴⁺, respectively. With the increase in the activator (Mn⁴⁺) concentration, the relationship between the luminescence decay time and the energy transfer efficiency of the sensitizer (Dy³⁺) was studied in detail. Finally, an LED device was fabricated using a 460 nm blue chip, and the as-obtained far-red emitting LMGO:Mn⁴⁺,Dy³⁺ phosphors for Wedelia chinensis cultivation. As expected, the as-fabricated plant growth LED-treated Wedelia chinensis cultured in the artificial climate box with overhead LEDs demonstrated that after 28 days of irradiation, the average plant growth rate and the total chlorophyll content were better than those of specimens cultured using the commercial R-B LED lamps, indicating that the as-prepared phosphor could have a potential application in the agricultural industry.     

Tuning the luminescence properties of Mn4+-activated CaYAlO4 phosphor by co-doping cations for indoor plant cultivation

To fulfil the demands of high-power plant growth lamps, cation co-doping is an effective way to tune the photoluminescence properties of manganese (Ⅳ)-activated aluminate phosphors. Therefore, we managed to synthesize a series of cations co-doped CaYAlO₄:xMn⁴⁺, mSr²⁺, M⁺ (M⁺ = Li⁺, Na⁺, and K⁺) (CYAO:Mn, Sr, M) far-red-emitting phosphors. The excitation spectrum of these phosphors contained two excitation bands, and the opposite effects of these two bands on the luminescence intensity have been observed with the increase of Mn⁴⁺ concentration. By adding 0.1 mol Sr²⁺ ions to replace Ca²⁺ site, the emission intensity and thermal stability of CYAO:Mn phosphors can be enhanced. Furthermore, the luminescence properties of CSYAO:Mn can be further improved by co-doping monovalent alkali metal ions to serve as charge compensators, the increased number of Mn⁴⁺ luminescence centers. Moreover, 0.6 mol% Na⁺ can increase the initial emission intensity of the phosphors by 117% as the best ratio. The characteristic emission spectrum of the phosphors CYAO:Mn,Sr,M correspond to the phytochrome P_FR of plants. These experiments and characterization results have certified that these phosphors have a potential application in indoor plants cultivation.     

Achieving highly efficient far-red emission from luminescence-ignorable Ca2MgTeO6:Mn4+ to Ca2-zLnzMgTe1-yWyO6:Mn4+ (Ln = La,Y, Gd) phosphors via solid solution and impurity doping strategies

The Mn⁴⁺-doped Ca2MgTeO6 (CMTO) far-red emitting phosphors with double perovskite-type structure were successfully synthesized. Upon near-ultraviolet (n-UV, 300 nm) light excitation, the as-prepared phosphors showed far-red light at 700 nm attributed to the ²E_g→⁴A_2g transition of Mn⁴⁺ ion. The doping concentration of the CMTO:xMn⁴⁺ samples was optimized to be 0.8 mol%. The relevant mechanism of concentration quenching was demonstrated as the dipole-dipole interaction. Furthermore, solid solution and impurity doping strategies were adopted to improve the far-red emission of the luminescence-ignorable CMTO:Mn⁴⁺ phosphor. Series of Ca₂MgTe_(1−y)W_yO₆:0.8 mol%Mn⁴⁺ (y = 0–100 mol%) solid solution and Ca_2−zLn_zMgTe_0.6W_0.4O₆:Mn⁴⁺ (Ln = La, Y, and Gd, z = 10 mol%) phosphors were synthesized through the above two strategies. The luminescence intensity of the optimal Ca_1.9Gd_0.1MgTe_0.6W_0.4O₆:Mn⁴⁺ phosphor was 13.7 times that of the CMTO:Mn⁴⁺ phosphor and 2.51 times that of red commercial phosphor K₂SiF₆:Mn⁴⁺. Notably, both CMTO:Mn⁴⁺ and Ca_1.9Gd_0.1MgTe_0.6W_0.4O₆:Mn⁴⁺ phosphors exhibited remarkable thermal stability compared with most Mn⁴⁺-doped phosphors. Finally, the highly efficient Ca_1.9Gd_0.1MgTe_0.6W_0.4O₆:Mn⁴⁺ phosphor was successfully applied in fabricating the warm white light diode (w-LED). This working along both lines strategy exhibited great potential for luminescence optimization of Mn⁴⁺-doped oxide phosphors.     

Luminescence enhancement of Mn4+-activated double-perovskite phosphors for LEDs through a co-replacement strategy

Phosphors doped with Mn⁴⁺ ions have strong emission in the red and far-red light regions and are therefore used as red phosphors for indoor plant cultivation light-emitting diodes (LEDs) and white LEDs (w-LEDs). This paper introduces La₂Mg(Mg_1/3Ta_2/3)O₆: Mn⁴⁺ (Mg₂La₃TaO₉: Mn⁴⁺) red phosphors prepared by conventional high-temperature solid-phase method. The broad excitation band of Mg₂La₃TaO₉: Mn⁴⁺ phosphor is effectively excited by ultraviolet and blue light in the range of 250–600 nm, with the emission of 707 nm centered on far-red light. The phosphor has a high color purity of 99.07% and an internal quantum efficiency of 59.87%. To further enhance the performance of the phosphor, a cation substitution method was adopted in this paper to synthesize La₂Mg(Al_1/2Ta_1/2)O₆: Mn⁴⁺ phosphor by replacing [1/3Mg²⁺–2/3Ta⁵⁺] in La₂Mg(Mg_1/3Ta_2/3)O₆: Mn⁴⁺ with [1/2Al³⁺–1/2Ta⁵⁺]. The luminescence intensity and thermal stability of the samples were enhanced. The emission spectrum of the Mg₂La₃TaO₉: Mn⁴⁺ samples matched well with the phytochrome P_FR (phytochrome that absorbs far-red light) and is suitable for the preparation of LEDs for indoor plant cultivation. The concentration quenching effect of the samples was investigated, the main mechanism of which is the electric dipole–dipole interaction. Red LEDs and w-LEDs devices were prepared with the synthesized phosphors that produce light stably at different currents. The w-LEDs have a correlated color temperature of 5310 K and a color rendering index of 80.1. Therefore, these samples are expected to be used as red components for w-LEDs.     

Deep-red emission of Mn4+ and Cr3+ in (Li1−xAx)2MgTiO4 (A=Na and K) phosphor: Potential application as W-LED and compact spectrometer

Mn⁴⁺ doped and Mn⁴⁺/Cr³⁺ co-doped alkali metal titanate phosphors have been prepared by solid state reaction method. A part of Li⁺ ions in the Li₂MgTiO₄: Mn⁴⁺ are substituted with Na⁺ and K⁺ ions and consequently the intensity of Mn⁴⁺ emission at 678 nm is enhanced by 1.7 and 2.5 times, respectively. In the Mn⁴⁺/Cr³⁺ co-doped (Li_0.95K_0.05)₂MgTi_0.999O₄, both emission of Cr³⁺at 726 nm and emission of Mn⁴⁺ at 678 nm of Mn⁴⁺ are observed. It is interesting to find that the intensity ratio of 726–678 nm emissions in the Mn⁴⁺/Cr³⁺ phosphor continually increases with excitation wavelength increasing from 290 nm to 455 nm, which means that the intensity ratio in turn can be used to identify the excitation light wavelength. This refers a possible approach to design novel compact light-wavelength detector or spectrometer based on the phosphor. The mechanism of Na⁺ or K⁺ substitution induced luminescence enhancement in the Mn⁴⁺ phosphor and the competition between the Cr³⁺ and Mn⁴⁺ emissions in the Mn⁴⁺/Cr³⁺ co-doped has been discussed.     

The role of co-dopants on the luminescent properties of α-Al2O3:Mn4+ and BaMgAl10O17:Mn4+

Mn⁴⁺ doped aluminate materials with efficient red emission are promising components for warmer white light-emitting diodes. However, it still remains as a challenge on increasing its luminous efficiency. For Mn⁴⁺ doped aluminate phosphors, co-dopants such as Li⁺, Mg²⁺, Na⁺, Si⁴⁺, or Ge⁴⁺ ions are often added to tailor the photoluminescence properties of phosphors during preparing process. However, the role of the ions is still in debate. In this work we took BaMgAl₁₀O₁₇:Mn (BMA:Mn) and α-Al₂O₃:Mn as examples to study the effects of Li⁺, Mg²⁺, Na⁺, and Si⁴⁺ on their luminescent properties. The energy levels induced by the co-dopants and some possible intrinsic defects of hosts (Al₂O₃) were calculated using the first-principles method. It is found that the Mg²⁺ and Na⁺ ions, compared with Li⁺ and Si⁴⁺, can prefer to form hole-type defects which enhance the valence stability of Mn⁴⁺ and thus enhance the emission intensity of the as-prepared phosphors.     

Crystal structure and luminescence properties of a single‐component white‐light‐emitting phosphor Ca8ZnLa(PO4)7:Eu2+,Mn2+

A series of novel green emission Whitlockite‐type Ca₈ZnLa(PO₄)₇:Eu²⁺ and color tunable Ca₈ZnLa(PO₄)₇:Eu²⁺,Mn²⁺ phosphors were prepared by the solid‐state reaction method in a reducing atmosphere. Its crystal structure and phase composition were identified by high‐resolution transmission electron microscopy, selected area electronic diffraction, X‐ray photoelectron spectroscopy, and X‐ray powder diffraction Rietveld refinement, and it was found to be trigonal, belonging to R‐3c(161) space group. The luminescence properties of Eu²⁺ singly doped and Eu²⁺/Mn²⁺ codoped Ca₈ZnLa(PO₄)₇ phosphors were revealed in detail. Ca₈ZnLa(PO₄)₇:Eu²⁺ is excitable over a broad range from 200 to 450 nm with a prominent green emitting. With varied Eu²⁺/Mn²⁺ ratios, fine‐tune emission under 365 nm excitation can be achieved from green (0.221, 0.468) to magenta (0.391, 0.276), especially the warm white light (0.392, 0.352), and CCT 3500 K can be obtained by the process of energy transfer between Eu²⁺ and Mn²⁺. The ET mechanism in this system is managed via the dipole‐dipole interaction with the maximum energy‐transfer efficiency 82.8% based on the decay lifetime data. These results suggest that as‐prepared phosphors can serve as promising candidates of UV‐pumped w‐LEDs.     

A novel far-red phosphors Li2ZnTi3O8:Cr3+ for indoor plant cultivation:Synthesis and luminescence properties

A novel far-red phosphors Li₂ZnTi₃O₈:Cr³⁺ were successfully synthesized via the conventional solid-state method. The structural characteristics, luminescence properties and concentration quenching of the Li₂ZnTi₃O₈:Cr³⁺ phosphors were investigated systematically. Under the excitation at 360 nm and 468 nm, the Li₂ZnTi₃O₈:Cr³⁺ phosphors displays the emission spectra in the range from 600 nm to 850 nm. The far-red emission centered at 735 nm was attributed to the spin-forbidden ²E→⁴A₂ transition of Cr³⁺ ions. The research results of this paper indicate that the phosphors Li₂ZnTi₃O₈:Cr³⁺ has prospective applications in indoor plant cultivation.     

Photoluminescence and energy transfer of efficient and thermally stable white-emitting Ca9La(PO4)7:Ce3+, Tb3+, Mn2+ phosphors

The development of novel single-component white-emitting phosphors with high thermal stability is essential for improving the illumination quality of white light-emitting diodes. In this work, we synthesized a series of Ce³⁺, Tb³⁺, Mn²⁺ single- and multiple-doped Ca₉La(PO₄)₇ (CLPO) phosphors with β-Ca₃(PO₄)₂-type structure by the simple high-temperature solid-state reaction. The crystallization behavior, crystal structure, surface morphology, photoluminescence performance, decay lifetime and thermal stability were systematically investigated. The PL spectra and decay curves have evidenced the efficient energy transfer from Ce³⁺ to Tb³⁺ and from Ce³⁺ to Mn²⁺ in the CLPO host, and corresponding energy transfer efficiency reaches 41.8% and 54.1%, respectively. The energy transfer process of Ce³⁺→Tb³⁺ and Ce³⁺→Mn²⁺ can be deduced to the resonant type via dipole-dipole and dipole-quadrupole interaction mechanism, and corresponding critical distance were determined to be 12.23 and 14.4 Å, respectively. Based on the efficient energy transfer, the white light emission can be successfully achieved in the single-component CLPO:0.15Ce³⁺, 0.10Tb³⁺, 0.04Mn²⁺ phosphor, which owns CIE chromaticity coordinates of (0.3245, 0.3347), CCT of 5878 K, internal and external quantum efficiency of 84.51% and 69.32%. Especially, compared with the emission intensity at 25 °C, it still remains 98.5% at 150 °C and 92.0% at 300 °C. Based on these results, the single-component white light emission phosphor CLPO:0.15Ce³⁺, 0.10Tb³⁺, 0.04Mn²⁺ is a potential candidate for UV-converted white LEDs.     

Enhanced narrow green emission and thermal stability in γ-AlON: Mn2+, Mg2+ phosphor via charge compensation

A series of novel green emitting γ-AlON: Mn²⁺, Mg²⁺ and γ-AlON: Mn²⁺, Mg²⁺, M (M?=?Li⁺, Na⁺, K⁺, Si⁴⁺) phosphors were fabricated with the gas-pressure sintering reaction process. The phase structure, morphology and photoluminescence properties of the phosphors were characterized via X-ray powder diffraction, scanning electron microscopy, and photoluminescence spectroscopy. Meanwhile, the charge compensation methods were utilized to eliminate the disadvantage of charge imbalance between Al³⁺ and Mn²⁺. The results show that the luminescence intensity of Mn²⁺ was maximally enhanced by the introduction of Si⁴⁺ ions, which was 2.36 times that of the sample without charge compensator. Moreover, as the temperature reached at 150?°C, thermal stability of the samples contained charge compensator Li⁺ and Si⁴⁺ were improved to 93% and 90% of that the room temperature, respectively, while the original sample was 85%. These luminescence properties were enhanced due to the introduction of charge compensators which reduce defects caused by charge imbalance. In addition, the specific mechanisms were discussed in detail. In general, the charge compensation could be used as an effective strategy to strengthen thermal stability and luminescence performances of phosphors.     

Luminescence of MgAl2O4 and ZnAl2O4 spinel ceramics containing some 3d ions

The luminescence properties of ceramic phosphors based on two spinel hosts MgAl₂O₄ and ZnAl₂O₄ doped with manganese ions have been studied. It has been found that the spectral properties of these phosphors can be strongly varied by changing synthesis conditions. Both types of doped ceramic spinel can serve as efficient Mn²⁺ green-emitting phosphors having peak emissions at 525 and 510 nm, respectively. Mn-doped MgAl₂O₄ spinel can also be prepared as an efficient Mn⁴⁺ red-emitting phosphor having peak emission at ~651 nm by using specific temperatures of heat treatment in air. It has also been shown that the conversion of Mn²⁺ to Mn⁴⁺ and viсe versa, as well as the coexistence of Mn²⁺ green and Mn⁴⁺ red emissions, can be accomplished by properly chosen annealing conditions of the same initially synthesized MgAl₂O₄:Mn sample. Manganese doped MgAl₂O₄ spinel with an optimal intensity ratio of green and red emissions can be a promising single-phase bicolor phosphor suitable for the development of warm white phosphor-converted LED lamps. On the other hand, it has been determined that perfectly normal ZnAl₂O₄ spinel cannot be doped with Mn⁴⁺ ions in contrast to partially inverse MgAl₂O₄ spinel. However, ZnAl₂O₄ samples unintentionally doped with impurity Cr³⁺ ions show emission spectra in the far-red region with well pronounced R, N and vibronic lines of Cr³⁺ luminescence due to the perfect normal spinel structure of synthesized ZnAl₂O₄ ceramics. Also, by partially substituting Al³⁺ cations for Mg²⁺ in ZnAl₂O₄ there is an opportunity to obtain Mn⁴⁺ doped or Mn⁴⁺/Cr³⁺ codoped far-red emitting phosphors which can be suitable for indoor plant growth lighting sources.     

Tuning the luminescence properties of blue and far-red dual emitting Gd2MgTiO6: Bi3+, Cr3+ phosphor for LED plant lamp

Blue and far-red light play a key role in plant growth, so it is necessary to develop blue and far-red dual emitting phosphors. However, the match between phosphors and plant pigments is not satisfactory. In this work, we synthesized a series of blue and far-red dual emission Gd₂MgTiO₆: Bi³⁺, Cr³⁺ (GMTO: Bi³⁺, Cr³⁺) phosphors and discussed the luminescence performance. The blue emission at 430 nm is ascribed to ³P₁ → ¹S₀ transition of Bi³⁺ and the far-red emission is ascribed to ⁴T₂ → ⁴A₂ and ²E → ⁴A₂ transitions of Cr³⁺. Notably, because of the energy competition between Cr³⁺ ions and host materials, the luminescence tuning realized with the content of Cr³⁺ doping. In addition, an energy-transfer performance occurred from Bi³⁺ ions to Cr³⁺ ions and the photoluminescence intensity of Cr³⁺ can be enhanced by Bi³⁺. The pc-LEDs devices were synthesized by GMTO: Bi³⁺, Cr³⁺ phosphor, and ultraviolet (UV) chips. Finally, the emission of GMTO: Bi³⁺, Cr³⁺ phosphor matched well with the absorption spectra of plant pigments which indicated the potential applications in LED plant lamp.     

Photoluminescence and temperature sensing of lanthanide Eu3+ and transition metal Mn4+ dual-doped antimoniate phosphor through site-beneficial occupation

For a long time, rare-earth ion-doped phosphors have been widely used in temperature sensing because of their excellent light-emitting properties. However, most of the rare earth elements are relatively rare and expensive, so the transition group elements that are economical and easy to obtain have been favored by researchers. This paper presents a new type of phosphor doped with rare earth ion and transition metal for optical temperature measurement. In recent years, Mn⁴⁺-doped phosphors have attracted wide attention because of their strong deep red light-emitting properties. La₂LiSbO₆ provides a good host environment for Mn⁴⁺ and Eu³⁺ due to its unique crystal structure. In this paper, a series of La₂LiSbO₆ phosphors singly doped with Mn⁴⁺ and Eu³⁺, and co-doped with Eu³⁺/Mn⁴⁺ were synthesized. The crystal phases and optical properties of these materials were characterized and analyzed in detail. We specifically studied the temperature dependence of the fluorescence intensity of the optimized La₂LiSbO₆: Eu³⁺, Mn⁴⁺ phosphors at 303K–523K. The experimental results prove that the thermal responses of Mn⁴⁺ and Eu³⁺ are different. With increasing temperature, the thermal quenching of the Mn⁴⁺ fluorescence intensity is much faster than that of Eu³⁺, so the temperature characteristics can be explored by the fluorescence intensity ratio (FIR) of Eu³⁺ to Mn⁴⁺. At 523 K, its maximum relative sensitivity and maximum absolute sensitivity can reach 0.891% K⁻¹ and 0.000264 K^-1, respectively. Our experimental analysis shows that La₂LiSbO₆:Eu³⁺/Mn⁴⁺ phosphors have relatively high temperature sensitivity and have potential application prospects in the field of high temperature sensing.     

Bi3+/Mn4+ co-doped dual-emission phosphors for potential plant lighting

Developing environment-friendly dual-emission phosphors of both blue–cyan and deep-red lights is desirable for the utilized indoor plant lighting research. Notably, the naked 6s and 6p Bi³⁺ ions are sensitive to the lattice sites, which emit from Ultraviolet (UV) to red lights in various crystal compounds. Meanwhile, the ²E → ⁴A_2g transition of Mn⁴⁺ ions promises its deep-red light emissions, which satisfies the demand for specific wavelength lights for plants growth. Hence, a Bi³⁺/Mn⁴⁺ co-doped Sr₂LaGaO₅: Bi³⁺, Mn⁴⁺ (SLGO:Bi³⁺:Mn⁴⁺) phosphor was finally synthesized. The phase, micromorphology and luminescent properties were systematically evaluated. Upon excitation at 350 nm light, dual emissions of both blue–cyan (470 nm) and deep-red (718 nm) lights were observed. Besides, due to the pronounced photoluminescence (PL) spectral overlap between Bi³⁺ and Mn⁴⁺ ions, a potential energy transfer process from Bi³⁺ to Mn⁴⁺ ions was confirmed. The relative PL intensities between Bi³⁺ and Mn⁴⁺ ions can be tuned just by adjusting the Mn⁴⁺ ion concentration. Besides, Li⁺ co-doping has been evidenced to improve the deep-red emissions (718 nm) of SLGO:0.005Mn⁴⁺ due to charge compensation and rationally designed lattice distortion, together with the improved thermal stability. Finally, the emissions of SLGO:Bi³⁺, Mn⁴⁺, Li⁺ phosphor suit properly with the absorption of the four fundamental pigments for plant growth, indicating that the prepared phosphorescent materials may have a prospect in plant light-emitting diodes lighting.     

Improving the luminescence properties and powder morphologies of red-emitting Sr0.8Ca0.19AlSiN3:0.01Eu2+ phosphors for high CRIs white LEDs by adding fluxes

Red-emitting Sr_0.8Ca_0.19AlSiN₃:0.01Eu²⁺ phosphor with halide fluxes for use in the production of white light-emitting diodes (white LEDs) with high-colour rendering indices (CRIs) was prepared through the high-temperature solid-state method. Fluoride (NaF, SrF₂, BaF₂, CaF₂, AlF₃·3H₂O and CeF₃), chloride (NH₄Cl, BaCl₂, MgCl₂, NaCl and LiCl) and composite fluxes (NaF + SrF₂, SrF₂+NH₄Cl and NaF + NH₄Cl) were applied in the phosphors. NaF, SrF₂, NH₄Cl and NaF + SrF₂ fluxes had prominent effects on the characteristics of Sr_0.8Ca_0.19AlSiN₃:0.01Eu²⁺ phosphors. Sr_0.8Ca_0.19AlSiN₃:0.01Eu²⁺ phosphors with various powder morphologies can be obtained through the addition of fluxes, which are conducive for phosphor formation. The powder morphologies of phosphors incorporated with NaF + SrF₂ were preferable to those of powders incorporated with other fluxes. This result indicated that the incorporation of NaF + SrF₂ into Sr_0.8Ca_0.19AlSiN₃:0.01Eu²⁺ yielded phosphors with high luminescent intensity and quantum efficiency, excellent thermal stability, narrow full widths at half-maximum (FWHM, 75.2 nm), uniform rod-like morphologies with large particle sizes (D₅₀ = 16.99 μm) and good particle dispersion. White LEDs with high CRIs were obtained by combining prepared phosphors (NaF + SrF₂ additive) with the commercial green-emitting phosphors Y₃(Al,Ga)₅O₁₂:Ce³⁺ and (Sr,Ba)₂SiO₄:Eu²⁺. White LEDs with Y₃(Al,Ga)₅O₁₂:Ce³⁺ and (Sr,Ba)₂SiO₄:Eu²⁺ phosphors had correlated colour temperatures (CCTs) of 3064 and 3023 K, respectively, and CRIs of 81.8 and 92.4, respectively. Therefore, NaF + SrF₂ can be used as a favourable flux for the production of Sr_0.8Ca_0.19AlSiN₃:0.01Eu²⁺.     

Engineering cation vacancies to improve the luminescence properties of Ca14Al10Zn6O35: Mn4+ phosphors for LED plant lamp

In the recent years, Mn⁴⁺-doped phosphors for indoor plant cultivation have received extensive concern owing to the far-red emission that can match well with the absorption spectra of plant pigments. Whereas, many Mn⁴⁺-doped phosphors still face some challenges such as poor light efficiency and low thermal stability. It is an effective way to resolve these problems via cation vacancies engineering. Herein, the Ca_14−xAl₁₀Zn_6−yO₃₅: Mn⁴⁺ phosphors are successfully synthesized by combustion method. The luminescence intensity of Ca_14−xAl₁₀Zn_6−yO₃₅: Mn⁴⁺ phosphor is enhanced through engineering Ca²⁺ and Zn²⁺ vacancies according to the charge compensation mechanism. The optimal content of each Ca²⁺ and Zn²⁺ vacancy is equal to be 0.3. Furthermore, the defect formation is accompanied with lattice distortion, which plays a vital role in driving the excited phonon traps to reduce the energy loss by non-radiation transitions. Therefore, the thermal stability of Ca_14−xAl₁₀Zn_6−yO₃₅: Mn⁴⁺ phosphor is also improved via engineering cation vacancies. In addition, the Ca_14−xAl₁₀Zn_6−yO₃₅: Mn⁴⁺ phosphors can be effectively excited by blue light and it exhibits far-red emission due to the Mn⁴⁺ spin-forbidden ²E → ⁴A₂ transition. The results suggest that the Ca_14−xAl₁₀Zn_6−yO₃₅: Mn⁴⁺ phosphors can have a tremendous potential in indoor plant cultivation.     

Synthesis,Structure, and Tunable Luminescence Properties of Novel Ba3NaLa(PO4)3F:Eu2+,Mn2+ Phosphors

A series of luminescent emission‐tunable phosphors Ba₃NaLa(PO₄)₃F:Eu²⁺,Mn²⁺ have been prepared by a high‐temperature solid‐state reaction. The Rietveld refinement analysis confirms that the obtained phosphors possess pure apatite crystalline phase and the sites' occupancy of dopant has been also discussed. Upon the excitation of 355 nm, the emission spectra of Ba₃NaLa(PO₄)₃F:Eu²⁺,Mn²⁺ consist of two broad bands assigned to 5d–4f transition of Eu²⁺ and ⁴T₁ (⁴G)–⁶A¹ (⁶S) transitions of Mn²⁺, respectively. Energy transfer (ET) occurs in Eu²⁺, Mn²⁺ codoped Ba₃NaLa(PO₄)₃F host. On the basis of the thorough analysis and comparison upon their excitation, emission properties, and the decay behaviors, it is demonstrated that the ET mechanism between Eu²⁺ and Mn²⁺ is ascribed to the exchange interaction, and the tunable emission color in the novel apatite host can be realized.     

Enhanced luminescence and energy transfer performance of double perovskite structure Gd2MgTiO6:Bi3+, Mn4+ phosphor for indoor plant growth LED lighting

Deep-red light emitting phosphors are widely used in LEDs for indoor plant growth because of the critical role played by red light in plant growth. The luminescence properties of deep-red phosphors are still not well understood at present. An energy transfer strategy is a common and effective method to improve luminescence properties. In principle, the energy transfer process may occur when the sensitizer's emission spectra overlap with the activator's excitation spectra. In this work, Bi³⁺ and Mn⁴⁺ were incorporated into the matrix of Gd₂MgTiO₆ as sensitisers and activators, respectively. Mn⁴⁺ ions tend to occupy the [TiO₆] octahedral site and the Bi³⁺ ions are expected to substituted in the site of Gd³⁺. The energy transfer process from Bi³⁺ to Mn⁴⁺ was realised and the photoluminescence (PL) intensity of Mn⁴⁺ increased with the doping content of Bi³⁺. Upon excitation at 375 nm, the PL intensity of Mn⁴⁺ increased to 116.4% when the doping concentration of Bi³⁺ reached 0.3%. Finally, the pc-LED devices were prepared by a Gd₂MgTiO₆:Bi³⁺, Mn⁴⁺ phosphor. The high red luminescence indicated that this phosphor has potential applications in indoor LED lighting.