Liangling Sun

High-efficiency and thermally stable far-red-emitting NaLaMgWO 6 :Mn 4+ phosphorsfor indoor plant growth light-emitting diodes

In this Letter, we report a novel NaLaMgWO6:Mn4+ double-perovskite phosphor. Under the excitation at 342xa0nm, this phosphor showed a high-efficiency far-red emission at approximately 700xa0nm with internal quantum efficiency of up to 60%. Moreover, it exhibited a high thermal stability; the emission intensity at 423xa0k was approximately 57% of that at room temperature. Finally, a prototype light-emitting diode (LED) device was fabricated using the combination of a NaLaMgWO6:Mn4+ far-red-emitting phosphor and 365-nm LED chip.

Novel Mn4+-activated LiLaMgWO6 far-red emitting phosphors: high photoluminescence efficiency, good thermal stability, and potential applications in plant cultivation LEDs

Double perovskite-based LiLaMgWO6:Mn4+ (LLMW:Mn4+) red phosphors were synthesized by traditional solid-state route under high temperature, and they showed bright far-red emission under excitation of 344 nm. The crystal structure, luminescence performance, internal quantum efficiency, fluorescence decay lifetimes, and thermal stability were investigated in detail. All samples exhibited far-red emissions around 713 nm due to the 2Eg → 4A2g transition of Mn4+ under excitation of near-ultraviolet and blue light, and the optimal doping concentration of Mn4+ was about 0.7 mol%. The CIE chromaticity coordinates of the LLMW:0.7% Mn4+ sample were (0.7253, 0.2746), and they were located at the border of the chromaticity diagram, indicating that the phosphors had high color purity. Furthermore, the internal quantum efficiency of LLMW:0.7% Mn4+ phosphors reached up to 69.1%, which was relatively higher than those of the reported Mn4+-doped red phosphors. Moreover, the sample displayed good thermal stability; the emission intensity of LLMW:0.7% Mn4+ phosphors at 423 K was 49% of the initial value at 303 K, while the activation energy was 0.39 eV. Importantly, there was a broad spectral overlap between the emission band of LLMW:Mn4+ phosphors and the absorption band of phytochrome PFR under near-ultraviolet light. All of these properties and phenomena illustrate that the LLMW:Mn4+ phosphors are potential far-red phosphors for applications in plant cultivation LEDs.

Synthesis and photoluminescence properties of novel far-red-emitting BaLaMgNbO6:Mn4+ phosphors for plant growth LEDs

A series of far-red-emitting BaLaMgNbO6:Mn4+ (BLMN:Mn4+) phosphors were successfully synthesized by a high-temperature solid-state reaction method. Crystal structure and luminescence properties of the obtained samples were systematically investigated. The emission spectra exhibited a strong narrow far-red emission band peaking at 700 nm with a full width at half-maximum (FWHM) of ∼36 nm under 360 nm excitation. The optimal Mn4+ concentration was about 0.4 mol%. The internal quantum efficiency and CIE chromaticity coordinates of the BLMN:0.4% Mn4+ phosphor were 52% and (0.7222, 0.2777), respectively. In addition, the luminescence mechanism has been analyzed using a Tanabe–Sugano energy level diagram. Finally, by using a 365 nm near-ultraviolet InGaN chip combined with BLMN:0.4% Mn4+ phosphors, a far-red LED device was fabricated.

Novel SrMg2La2W2O12:Mn4+ far-red phosphors with high quantum efficiency and thermal stability towards applications in indoor plant cultivation LEDs

Novel Mn4+-activated far-red emitting SrMg2La2W2O12 (SMLW) phosphors were prepared by a conventional high-temperature solid-state reaction method. The SMLW:Mn4+ phosphors showed a broad excitation band peaking at around 344 nm and 469 nm in the range of 300–550 nm. Under 344 nm near-ultraviolet light or 469 nm blue light, the phosphors exhibited a far-red emission band in the 650–780 nm range centered at about 708 nm. The optimal Mn4+ doping concentration in the SMLW host was 0.2 mol% and the CIE chromaticity coordinates of SMLW:0.2% Mn4+ phosphors were calculated to be (0.7322, 0.2678). In addition, the influences of crystal field strength and nephelauxetic effect on the emission energy of Mn4+ ions were also investigated. Moreover, the internal quantum efficiency of SMLW:0.2% Mn4+ phosphors reached as high as 88% and they also possessed good thermal stability. Specifically, the emission intensity at 423 K still maintained about 57.5% of the initial value at 303 K. Finally, a far-red light-emitting diode (LED) lamp was fabricated by using a 365 nm near-ultraviolet emitting LED chip combined with the as-obtained SMLW:0.2% Mn4+ far-red phosphors.

Novel SrLaAlO4:Mn4+ deep-red emitting phosphors with excellent responsiveness to phytochrome PFR for plant cultivation LEDs: synthesis, photoluminescence properties, and thermal stability

Herein, novel rare-earth-free Mn4+-doped SrLaAlO4 deep-red emitting phosphors were successfully synthesized via a traditional solid-state reaction method. The crystal structure and phase purity of the as-prepared samples were confirmed by XRD Rietveld refinement. Photoluminescence properties of SrLaAlO4:Mn4+ phosphors were examined in detail using photoluminescence spectra, decay lifetimes, temperature-dependent emission spectra and internal quantum efficiency measurements. The excitation spectrum obtained by monitoring at 730 nm contained two excitation bands centered at 364 and 520 nm within the range of 200–550 nm due to the Mn4+–O2− charge-transfer band and the 4A2g → 4T1g, 4T2g transitions of the Mn4+ ions. Under the 364 nm excitation, the SrLaAlO4:Mn4+ phosphors exhibited an intense deep-red emission band in 610–790 nm wavelength range peaking at 730 nm, which was assigned to the 2Eg → 4A2g transition of Mn4+ ions. The deep red emission showed excellent responsiveness to phytochrome PFR, revealing that the SrLaAlO4:0.4% Mn4+ phosphors possessed a possible application in deep-red light-emitting diodes (LEDs) for plant cultivation. The optimal doping concentration of Mn4+ ions was found to be 0.4 mol%. The critical distance Rc for energy transfer among Mn4+ ions was determined to be 5.86 A and the concentration quenching mechanism was confirmed to be the electric dipole–dipole interaction. In addition, the Commission International de IEclairage (CIE) colour coordinates of the SrLaAlO4:0.4% Mn4+ phosphors (0.734, 0.266) were located in the deep red region and the corresponding internal quantum efficiency was measured to be about 29%. The above results confirmed that the as-prepared SrLaAlO4:0.4% Mn4+ deep red emitting phosphors might be a potential candidate for plant cultivation LEDs.

Synthesis and characterization of Ca3Lu(GaO)3(BO3)4:Ce3+,Tb3+ phosphors: tunable-color emissions, energy transfer, and thermal stability

Blue-green dual-emitting phosphors Ca3Lu(GaO)3(BO3)4:Ce3+,Tb3+ (CLGB:Ce3+,Tb3+) were synthesized via a traditional solid-state reaction method. The phase of the phosphors was characterized by X-ray diffraction and the luminescence properties were investigated using the excitation and emission spectra, decay curves, temperature-dependent emission spectra, CIE chromaticity coordinates, and the internal quantum efficiency. Under 345 nm UV light excitation, Ce3+ singly doped CLGB phosphors presented intense blue light in the 350–550 nm wavelength region with a maximum peak at 400 nm. In sharp contrast, CLGB:Ce3+,Tb3+ phosphors showed both the blue and green emission wavelengths of Ce3+ and Tb3+ ions, respectively. The overall emission colors can be tuned from blue (0.164, 0.042) to green (0.331, 0.485) via increasing the concentration of Tb3+ ions, due to the energy transfer (ET) from Ce3+ ions to Tb3+ ions. The optimal doping concentration of Tb3+ ions in CLGB:Ce3+,Tb3+ phosphors was found to be 40 mol%. The mechanism of the ET from the Ce3+ to Tb3+ ions was demonstrated to be electric quadrupole–quadrupole interaction. The CLGB:0.04Ce3+,0.40Tb3+ sample possessed a high IQE of 54.2% and excellent thermal stability with an activation energy of 0.3142 eV when excited at 345 nm. The integrated emission intensity of CLGB:0.04Ce3+,0.40Tb3+ at 423 K was found to be about 74% of that at 303 K. Finally, under 300 mA driven current, the fabricated prototype white light-emitting diode showed CIE chromaticity coordinates of (0.3996, 0.3856) and high color rending index of 81.2. Considering all the above characteristics, the obtained CLGB:Ce3+,Tb3+ phosphors can be a type of multicolor emitting phosphor for application in white light-emitting diodes.

Novel Eu3+-activated Ba2Y5B5O17 red-emitting phosphors for white LEDs: high color purity, high quantum efficiency and excellent thermal stability

Eu3+-activated Ba2Y5B5O17 (Ba2Y5−xEuxB5O17; x = 0.1–1) red-emitting phosphors were synthesized by the conventional high temperature solid-state reaction method in an air atmosphere. Powder X-ray diffraction (XRD) analysis confirmed the pure phase formation of the as-synthesized phosphors. Morphological studies were performed using field emission-scanning electron microscopy (FE-SEM). The photoluminescence spectra, lifetimes, color coordinates and internal quantum efficiency (IQE) as well as the temperature-dependent emission spectra were investigated systematically. Upon 396 nm excitation, Ba2Y5−xEuxB5O17 showed red emission peaking at 616 nm which was attributed to the 5D0 → 7F2 electric dipole transition of Eu3+ ions. Meanwhile, the influences of different concentrations of Eu3+ ions on the PL intensity were also discussed. The optimum concentration of Eu3+ ions in the Ba2Y5−xEuxB5O17 phosphors was found to be x = 0.8. The concentration quenching mechanism was attributed to the dipole–dipole interaction and the critical distance (Rc) for energy transfer among Eu3+ ions was determined to be 5.64 A. The asymmetry ratio [(5D0 → 7F2)/(5D0 → 7F1)] of Ba2Y4.2Eu0.8B5O17 phosphors was calculated to be 3.82. The fluorescence decay lifetimes were also determined for Ba2Y5−xEuxB5O17 phosphors. In addition, the CIE color coordinates of the Ba2Y4.2Eu0.8B5O17 phosphors (x = 0.653, y = 0.345) were found to be very close to the National Television System Committee (NTSC) standard values (x = 0.670, y = 0.330) of red emission and also showed high color purity (∼94.3%). The corresponding internal quantum efficiency of the Ba2Y4.2Eu0.8B5O17 sample was measured to be 47.2%. Furthermore, the as-synthesized phosphors exhibited good thermal stability with an activation energy of 0.282 eV. The above results revealed that the red emitting Ba2Y4.2Eu0.8B5O17 phosphors could be potential candidates for application in near-UV excited white light emitting diodes.

Synthesis and photoluminescence characteristics of high color purity Ba3Y4O9:Eu3+ red-emitting phosphors with excellent thermal stability for warm W-LED application

Single phase Eu3+-activated Ba3Y4O9 (Ba3(Y1−xEux)4O9) red-emitting phosphors with different Eu3+ doping concentrations were synthesized by a high temperature solid-state reaction method. The phase purity, crystal structure, photoluminescence properties, internal quantum efficiency, decay lifetimes, and thermal stability were investigated. Upon excitation at 396 nm near-ultraviolet light and 469 nm blue light, the Ba3(Y1−xEux)4O9 phosphors exhibited a strong red emission at 614 nm due to the 5D0 → 7F2 transition of Eu3+ ions. The optimal doping concentration of Eu3+ ions in Ba3(Y1−xEux)4O9 was found to be x = 0.25. Furthermore, the critical distance was calculated to be 12.78 A and the energy transfer mechanism for the concentration quenching effect was determined to be quadrupole–quadrupole interaction. In addition, the Commission Internationale de IEclairage (CIE) chromaticity coordinates of Ba3(Y0.75Eu0.25)4O9 phosphors were measured to be (0.6695, 0.3302) which located at the red region, and significantly, the high color purity was about 97.9%. The as-synthesized phosphors also possessed excellent thermal stability and the activation energy was determined to be 0.29 eV. Therefore, the investigated results indicated that the Ba3Y4O9:Eu3+ phosphor may be a suitable candidate as a red phosphor for white light-emitting diodes under effective excitation at near-ultraviolet and blue light.

Preparation, characterization, and luminescence properties of double perovskite SrLaMgSbO6:Mn4+ far-red emitting phosphors for indoor plant growth lighting

Mn4+-activated SrLaMgSbO6 far-red emitting phosphors with double perovskite structure were prepared by traditional solid-state reaction. The research on the crystal structure of the SrLaMgSbO6:0.8%Mn4+ (SLMS:0.8%Mn4+) phosphors showed that the as-prepared sample was made up of two polyhedrons, [SbO6] and [MgO6]. Under the excitation of 333 nm, the SLMS:0.8%Mn4+ phosphors exhibited an intense far-red emission in the 625–800 nm wavelength range with CIE chromaticity coordinates of (0.733, 0.268), which could match well with the absorption spectrum of phytochrome PFR. The optimal concentration of Mn4+ ions in the SLMS:Mn4+ phosphors was 0.8 mol%. Importantly, the as-prepared SLMS:0.8%Mn4+ phosphors had an internal quantum efficiency of 35%. The thermal stability of SLMS:0.8%Mn4+ phosphors was also investigated, and the activation energy was found to be 0.3 eV. Thus, the Mn4+-activated SLMS phosphors have great potential to serve as far-red emitting phosphors in indoor plant growth lighting.

Novel high-efficiency Eu3+-activated Na2Gd2B2O7 red-emitting phosphors with high color purity

In this study, a series of Na2(Gd1−xEux)2B2O7 (abbreviated as: Na2Gd2B2O7:xEu3+; x = 0, 0.05, 0.15, 0.35, 0.45, and 0.50) phosphors were synthesized by conventional solid state reaction approach. The structure and morphology of the as-prepared phosphors were studied by X-ray diffraction, scanning electron microscopy and elemental mapping. The results indicated that the phosphors had micro-size particles with monoclinic phases. The photoluminescence excitation and emission study indicated that the as-prepared phosphors could give rise to efficient red emissions under near-ultraviolet excitation. The optimal doping concentration of Eu3+ ions was x = 0.35, and the corresponding deduced critical distance (Rc) was about 9.4 A. The concentration quenching mechanism was dominated by energy-transfer among the Eu3+ ions through dipole–dipole interactions. The calculated internal quantum efficiency of the Na2Gd2B2O7:0.35Eu3+ red phosphor was 70.8% and the color purity was as high as 99%. Furthermore, decay dynamics revealed that with the increase in the content of Eu3+, the lifetimes decreased due to the increase in non-radiative transition. Importantly, the present Na2Gd2B2O7:0.35Eu3+ phosphors also exhibited good thermal stability, and the emission intensity at 150 °C was about 56% of that at 30 °C. Furthermore, a warm white light-emitting diode (WLED) device was fabricated with commercial BaMgAl10O17:Eu2+ blue phosphors, (Ba,Sr)2(SiO4):Eu2+ green phosphors, and the as-prepared Na2Gd2B2O7:0.35Eu3+ red phosphors as well as a 395 nm LED chip. The device exhibited CIE coordinates of (0.4367, 0.3987), a high color rendering index (CRI = 92.2), a low correlated color temperature (CCT = 2960 K), and a luminous efficacy of 40.65 lm W−1. The observed results strongly indicate that the as-prepared Na2Gd2B2O7:Eu3+ phosphors may be used as the red emitting component in pc-WLEDs.