Effects of HfO2 dopant on characteristics of Li2MgTiO4-based red phosphors: Thermal stability,photoluminescence intensity and quantum efficiency improvement

To produce natural and vivid color, the color rendering index of white light-emitting diodes (WLEDs) with single phosphors is usually lower than 70, which is problematic for LED applications. A commonly used method to resolve this issue is to enhance the red component of WLEDs. In the present study, Hf⁴⁺ and Mn⁴⁺ co-doped Li₂MgTiO₄ red phosphors are synthesized using a solid-state reaction method. When this red phosphor is excited at 397 and 468?nm, it exhibits weak reabsorption in the blue region and emits a broad and deep red emission band in the range of 640–750?nm, which is attributed to the ²E_g → ⁴A_2?g transition. With 5?mol% HfO₂ dopant, the photoluminescence intensity is enhanced by 1.45-fold and thermal stability is increased by 7.7%. Moreover, this red phosphor was applied to a red phosphor-in-glass (RPiG) optical device with a low-melting TeO₂-B₂O₃-ZnO-Na₂O-WO₃ glass system. In the RPiG melting process, Li₂MgTiO₄:Mn⁴⁺, Hf⁴⁺ red phosphor triggered neither a chemical reaction nor severe degradation, indicating good thermal stability. Li₂MgTiO₄:Mn⁴⁺, Hf⁴⁺ has potential as a red emission material for warm WLED applications.     

LiCa3MgV3O12:Sm3+: A new high-efficiency white-emitting phosphor

A novel single-phased white-light-emitting phosphor Sm³⁺ doped LiCa₃MgV₃O₁₂ (LCMV) was developed. The LCMV host was one self-activated bluish-green emitting phosphor, which possessed an efficient excitation band in the 250–400?nm wavelength range and showed an intense broadband bluish-green emission with internal quantum efficiency (IQE) of 39%. Doping Sm³⁺ ions in to LCMV host induced tunable-color emissions, due to the energy transfer from [VO₄]^3? to Sm³⁺ ions. Importantly, under 340?nm excitation, the LCMV:Sm³⁺ can emitted bright white light by combining the self-activated luminescence of LCMV host and the red emissions of Sm³⁺ ions, and the IQE of the white-emitting composition-optimized LCMV:0.01Sm³⁺ phosphors reached up to 45%. These white-emitting LCMV:Sm³⁺ phosphors have potential applications in white light-emitting diodes and optical display devices.     

Mn4+-activated KLaMgWO6: A new high-efficiency far-red phosphor for indoor plant growth LEDs

Novel Mn⁴⁺-activated KLaMgWO₆ red phosphors with different Mn⁴⁺ concentrations were successfully synthesized via a high-temperature solid-state reaction method. The phase formation, microstructure, photoluminescence properties, decay lifetimes and internal quantum efficiency were discussed to analyze the properties of the as-prepared phosphors. The samples belonged to monoclinic crystal system with enough WO₆ octahedrons that provided suitable sites for Mn⁴⁺ ions. Upon the excitation of 348?nm, KLaMgWO₆:Mn⁴⁺ phosphors gave bright far-red emission around 696?nm due to the ²E_g→⁴A_2g transition of Mn⁴⁺ ions. The critical concentration of Mn⁴⁺ was 0.6?mol% and the concentration quenching mechanism belonged to electric multipolar interaction. Besides, the CIE chromaticity coordinates of the KLaMgWO₆:0.6%Mn⁴⁺ phosphor were (0.7205, 0.2794) which located in deep red range, and its color purity reached up to 96.6%. The KLaMgWO₆:0.6%Mn⁴⁺ sample also exhibited high internal quantum efficiency of 43%. All of the admirable optical properties indicate that the KLaMgWO₆:Mn⁴⁺ phosphors can be applied to indoor plant growth illumination.     

Synthesis and photoluminescence properties of a novel red phosphor SrLaGaO4:Mn4+

A novel Mn⁴⁺-doped strontium lanthanum gallate red phosphor SrLaGaO₄:Mn⁴⁺ has been successfully prepared via the conventional solid-state reaction method. Phase purity, photoluminescence excitation/emission spectra, concentration quenching, decay curves, and temperature-dependent photoluminescence have been investigated systematically. SrLaGaO₄:Mn⁴⁺ phosphor exhibits broad excitation band from 250 to 600 nm and emits intense red light centered at 716 nm arising from spin-forbidden transition, ²E → ⁴A₂ of Mn⁴⁺. The optimal dopant concentration of Mn⁴⁺ is determined to be 0.2 mol%. Dipole-dipole interaction is supposed to be the mechanism of concentration quenching. The crystal-field strength Dq, the Racah parameters B and C, and the nephelauxetic ratio β₁ of SrLaGaO₄:Mn⁴⁺ have been calculated according to its luminescent spectra. Our systematic investigation on this new phosphor can provide a reference for the development of red-emitting phosphor.     

Fluorescence improvement of Ba1.3Ca0.7SiO4:Eu,Mn phosphors via Dy addition and their color-tunable properties

A series of novel single-phase white phosphors Ba_1.3Ca_0.69−x−ySiO₄:0.01Eu²⁺,xMn²⁺, yDy³⁺ were synthesized by the solid-state method. The excitation spectra of these phosphors exhibit a broad band in the range of 260–410 nm, which can meet the application requirements for near-UV LED chips (excited at 350–410 nm). The emission spectra consist of two broad bands positioned around 455 nm and 596 nm, which are assigned to 5d→4f transition of Eu²⁺, and ⁴T₁→⁶A₁ transition of Mn²⁺, respectively. The luminescence intensity of phosphors enhances obviously by doping Dy³⁺ ions, and the intensity of two bands reaches an optimum when Dy³⁺ amounts to 2 mol%. In addition, thermoluminescence investigation of phosphor was conducted, getting two shallow trap defects with activation energy of 0.43 eV and 0.45 eV, which demonstrates the energy transfer mechanism of Dy–Eu through the process of hole and electron traps. By precisely tuning the Mn²⁺ content, an optimized white light with color rendering index (CRI) of R_a=84.3%, correlated color temperature (CCT) of T_c=8416 K and CIE chromaticity coordinates of (0.2941, 0.2937) is generated. The phosphor could be a potential white phosphors for near-UV light emitting diodes.     

Deep-red-emitting SrLaLiTeO6: Mn4+ double perovskites: Correlation between Mn4+-O2− bonding and photoluminescence

Mn⁴⁺-activated deep red-emitting SrLaLiTeO₆ phosphors are investigated for indoor plant growth LED applications for the first time. The phosphors crystallize in monoclinic (P2₁/n) symmetry is isostructural with SrLaLiTeO₆ host. B-site substitution of Mn⁴⁺ ions is confirmed from the redshift of high energy phonon modes in both Raman and IR spectra. The phosphor exhibited a far-red emission centered at 696 nm corresponding to the ²E_g → ⁴A_2g spin-forbidden transition of the Mn⁴⁺ ions. Approximate crystal field parameters depict the weak influence of neighboring ligand fields on Mn⁴⁺ ions and the least covalence of Mn⁴⁺-ligand bonding compared to other double perovskite phosphors. Moreover, the phosphors exhibit excellent thermal stability with an activation energy of 0.23 eV. Phosphor parameters including CCT, color purity, and quantum yield are evaluated and their values meet the requirements of a red-emitting phosphor for LED applications. Furthermore, the PL emission spectrum of SrLaLiTeO₆: Mn⁴⁺ matches with the absorption spectrum of plant phytochromes denoting the prospects of this phosphor for indoor plant growth LED applications.     

A far-red-emitting (Gd,Y)3(Ga,Al)5O12:Mn2+ ceramic phosphor with enhanced thermal stability for plant cultivation

As for plants, far-red (FR) light with wavelength from 700 nm to 740 nm is critical for processes of photosynthesis and photomorphogenesis. Light-controlled development depends on light to control cell differentiation, structural and functional changes, and finally converge into the formation of tissues and organs. Phosphor converted FR emission under LED excitation is a cost-effective and high-efficient way to provide artificial FR light source. With the aim to develop an efficient FR phosphor that can promote the plant growth, a series of gadolinium yttrium gallium garnet (GYGAG) transparent ceramic phosphors co-doped with Mn²⁺ and Si⁴⁺ have been fabricated via chemical co-precipitation method, followed sintered in O₂ and hot isostatic pressing in this work. Under UV excitation, the phosphor exhibited two bright and broadband red emission spectra due to Mn²⁺: ⁴T₁ → ⁶A₁ spin-forbidden transition, and one of which located in the right FR region. And then, Ce³⁺ ions were co-doped as the activator to enhance the absorption at blue light region and the emission of Mn²⁺. It turns out that the emission band of GYGAG transparent ceramic phosphors matches well with the absorption band of phytochrome P_FR, which means they are promising to be applied in plant cultivation light-emitting diodes (LEDs) for modulating plant growth. Besides, the thermal stability of this material was investigated systematically, and an energy transferring model involves defects was also proposed to explain the phenomenon of abnormal temperature quenching.     

Tunable luminescence properties and efficient energy transfer in Eu,Mn co-doped Ba2MgP4O13

A series of Ba₂Mg_1−xMn_xP₄O₁₃ (x = 0-1.0) and Ba_1.94Eu_0.06Mg_1−xMn_xP₄O₁₃ (x = 0-0.15) phosphors were prepared by conventional solid-state reaction. X-ray powder diffraction (XRD), the photoluminescence spectra, and the decay curves are investigated. XRD analysis shows that the maximum tolerable substitution of Mn²⁺ for Mg is about 50 mol% in Ba₂MgP₄O₁₃. Mn²⁺-singly doped Ba₂MgP₄O₁₃ shows weak red-luminescence peaked at about 615 nm. The Eu²⁺/Mn²⁺ co-doped phosphor emits two distinctive luminescence bands: a blue one centered at 430 nm originating from Eu²⁺ and a broad red-emitting one peaked at 615 nm from Mn²⁺ ions. The luminescence of Mn²⁺ ions can be greatly enhanced with the co-doping of Eu²⁺ in Ba₂MgP₄O₁₃. The efficient energy transfer from Eu²⁺ to Mn²⁺ is verified by the excitation and emission spectra together with the luminescence decay curves. The emission colors could be tuned from the blue to the red-purple and eventually to the deep red. The resonance-type energy transfer via a dipole-quadrupole interaction mechanism is supported by the decay lifetime data. The energy transfer efficiency and the critical distance are calculated and discussed. The temperature dependent luminescence spectra of the Eu²⁺/Mn²⁺ co-doped phosphor show a good thermal stability on quenching effect.     

Eu2+-activated blue-emitting glass phosphor derived from Eu3+ exchanged USY zeolites by thermal treatment in reducing atmosphere

In this work, we report a facile method to prepare Eu²⁺ activated blue-emitting glass phosphor via loading Eu³⁺ into USY (Na₂₈Si₁₆₈Al₂₈O₃₈₄·240H₂O, Si/Al ratio=6) zeolites’ cavities followed by thermal treatment in reducing atmosphere. The zeolites powders containing Eu³⁺ were treated at different temperatures from 800?°C to 1200?°C in flowing 5%H₂ +?95%N₂ ambient. The photoluminescence properties were investigated on aspects of the emission and excitation spectra, internal quantum efficiency (IQE), thermal stability and the fluorescence lifetime. The XRD patterns showed that the sample calcined at 950?°C was of pure glassy state. Under the broad 200–430?nm excitation, a strong blue emission band peaked at 451?nm with a full width of half maximum (FWHM) value of 74?nm was observed for this sample. Under the 365?nm excitation, the samples treated at different temperatures showed monotone red shift in the emission peak wavelengths with the thermal treatment temperature increasing. Transparent glass sheets were obtained from the glass phosphor powders by spark plasma sintering (SPS) at 1200?°C, 1250?°C and 1300?°C. The optical transmittance and thermal conductivity of transparent glass sheets were measured. The results indicated that this glass phosphor may be a potential candidate material for white LEDs.     

Novel deep-red-emitting double-perovskite type Ca2ScNbO6:Mn4+ phosphor: Structure,spectral study,and improvement by NaF flux

A novel deep-red-emitting phosphor Ca₂ScNbO₆:Mn⁴⁺ is prepared via a high-temperature solid-state reaction and its luminescent properties are systematically investigated. The results show that Mn⁴⁺-activated Ca₂ScNbO₆ phosphors have broad absorption in ultraviolet region, and show bright deep-red emission at 692 nm. The optimal doping concentration, crystal-field strength, internal quantum efficiency, and mechanism of concentration and thermal quenching effects are discussed in detail. Moreover, NaF flux is screened out to improve both luminescent intensity and morphology of the phosphor. Finally, a red light-emitting diode (LED) lamp is fabricated with as-prepared Ca₂ScNbO₆:Mn⁴⁺ phosphors and a 365 nm LED chip. The electroluminescence spectra show a good overlapping with phytochrome P_R and P_FR absorbance. The results provided the as-synthesized Ca₂ScNbO₆:Mn⁴⁺ phosphors a great potential in plant growth lighting.     

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.     

Efficient and tunable Mn2+ sensitized luminescence via energy transfer of a novel red phosphor Ca19Mn2(PO4)14: Eu2+ for white LED

The exploration of efficient and high-purity red phosphors is an urgent need in LED development. Due to the compact and compositional-tunable structure of whitlockite compound, manganese-based Ca₁₉Mn₂(PO₄)₁₄ is chosen as phosphor host for Eu²⁺ sensitization. Rietveld refinement, steady-state spectra, decay lifetime analysis and temperature-dependent emission spectra were investigated and clearly discussed. Under 360 nm excitation, Ca₁₉Mn₂(PO₄)₁₄: Eu²⁺ shows a strong Mn²⁺ sensitized emission at 655 nm with FWHM of 82 nm, benefiting from the short-distance-induced high-efficient Eu² -Mn²⁺ energy transfer. Emission engineering of Ca₁₉Mn₂(PO₄)₁₄: Eu²⁺ is achieved by Sr²⁺ co-doping, leading to both tunable peak wavelength (ranging from 650 to 610 nm) and improved intensity (130% of original value). Moreover, Ca₁₉Mn₂(PO₄)₁₄: Eu²⁺ exhibits a promising thermal stability where only 40% of emission intensity is lost at 200 °C. Finally, we explored the working performance of the fabricated RGB phosphor-converted white LED. The present work indicates that Ca₁₉Mn₂(PO₄)₁₄: Eu²⁺ phosphor is of great potential as a promising and efficient red phosphor in phosphor-converted white LED.     

A double-perovskite Sr2ZnWO6:Mn4+ deep red phosphor: Synthesis and luminescence properties

Novel double-perovskite Sr₂ZnWO₆:Mn⁴⁺(SZW:Mn⁴⁺) phosphor is synthesized by high-temperature solid-state reaction method in air. SZW:Mn⁴⁺ phosphor with excitation at 325 and 526 nm emits deep-red light, the chromaticity coordinate is (0.7315,0.2685), and the emission band peaking at ~702 nm within the range 640–760 nm is assigned to the ²E→⁴A₂ transition of Mn⁴⁺ ion. The influences of “Mn⁴⁺- ligand” bonding and crystal field strength to emission properties of Mn⁴⁺ ion are analyzed. The optimal Mn⁴⁺ ion concentration in SZW:Mn⁴⁺ phosphor is ~0.8 mol%. Lifetime of SZW:Mn⁴⁺ phosphor decreases from 554.77 to 401.35 μs with increasing Mn⁴⁺ ion concentration in the range of 0.2–1.0 mol%. The lifetime data and decay curves indicate that there is only a single type of Mn⁴⁺ ion luminescent center in SZW:Mn⁴⁺ phosphor. The luminous mechanism of SZW:Mn⁴⁺ phosphor is analyzed by Tanabe-Sugano energy level diagram of Mn⁴⁺ in the octahedron together with the simple energy level diagram. The experimental results are helpful to research the influences of the neighboring coordination environment around Mn⁴⁺ and host crystal structure to the luminescence properties of Mn⁴⁺ ion and to deeply understand other Mn⁴⁺-dopedmaterials.     

Rare-earth-free Li5La3Ta2O12:Mn4+ deep-red-emitting phosphor: Synthesis and photoluminescence properties

Li₅La₃Ta₂O₁₂:Mn⁴⁺ (LLTO:Mn⁴⁺) phosphors are prepared in air via high-temperature solid-state method and investigated for their crystal structures and luminescence properties. LLTO:Mn⁴⁺ phosphor under excitation at 314 nm shows deep-red emission peaking at 714 nm due to the ²E→⁴A₂ transition of Mn⁴⁺ ion. The excitation bands in the range 220 - 570 nm are attributed to the Mn⁴⁺ - O^2- charge-transfer band and the ⁴A_2g→⁴T_1g, ²T_2g, and ⁴T_2g transitions of Mn⁴⁺, respectively. The optimal Mn⁴⁺ ion concentration is ~0.4 mol%. The concentration quenching mechanism in LLTO:Mn⁴⁺ phosphor is electric dipole-dipole interaction. The luminous mechanism and temperature quenching phenomenon are explained by the Tanabe-Sugano energy level diagram and the configurational coordinate diagram of Mn⁴⁺ in the octahedron, respectively. The experimental results indicate that LLTO:Mn⁴⁺ phosphor has a potential application prospect as candidate of deep-red component in light-emitting diode (LED) lighting.     

Enhancing photoluminescence properties of Mn4+-activated Sr4−xBaxAl14O25 red phosphors for plant cultivation LEDs

Non–rare earth Mn⁴⁺-activated strontium aluminate phosphor is considered to be a promising material for plant cultivation field owing to their advantage of inexpensively, environment friendly, nontoxic, and appropriate spectral range. In this paper, a Sr_4−xBa_xAl_13.99O₂₅:0.01Mn⁴⁺,1.4H₃BO₃ strontium aluminate phosphor is synthesized by a convenient high-temperature solid-state reaction. The photoluminescence spectra located at red region with a peak at 655 nm in the range of 600 to 750 nm that can be excited under the excitation of ultraviolet (~346 nm) or blue light (~450 nm). The shape emission band at 655 nm is attributed to the transition of ²E_g-⁴A_2g. Furthermore, the emission intensity of Sr_4−xBa_xAl_13.99O₂₅: 0.01Mn⁴⁺,1.4H₃BO₃ phosphor is conducted in detail with the variety of Ba²⁺ doping concentration and the intensity can be enhanced to 140.9% than the Sr₄Al_13.99O₂₅:0.01Mn⁴⁺,1.4H₃BO₃ when the value of Ba²⁺ concentration equal to 0.1 mol. In addition, the X-ray diffraction spectra, element mapping, composition modifying, optical properties, FT-IR spectra, diffuse reflectance spectra, thermal stability, and fluorescence lifetime are systematically investigated. According to the electro-luminescent spectra of as-packaged LED, indicating that the Sr_3.9Ba_0.1Al_13.99O₂₅:0.01Mn⁴⁺,1.4H₃BO₃ phosphor will become a great candidate for plant cultivation LEDs due to the emission spectra match well the plant pigment spectrum.     

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.     

Color tunable Ba3Lu(PO4)3:Tb3+,Mn2+ phosphor via Tb3+→Mn2+ energy transfer for white LEDs

Series of UV excited Ba₃Lu(PO₄)₃:Tb³⁺,Mn²⁺ phosphors with tunable green to red emissions had been prepared using solid state reactions. Powder X-ray diffraction and Rietveld structure refinement were used to investigate the phase purity and crystal structure of the prepared samples. Under UV excitation, the Ba₃Lu(PO₄)₃:Tb³⁺,Mn²⁺ samples exhibited not only the typical Tb³⁺ emission peaks but also the broad emission band of Mn²⁺ ions due to the efficient Tb³⁺→Mn²⁺ energy transfer which had been verified by luminescence spectra and decay curves. Utilizing the Inokuti-Hirayama model, the Tb³⁺→Mn²⁺ energy transfer mechanism was determined to be the electronic dipole–quadrupole interaction. Moreover, the emission spectra of Ba₃Lu(PO₄)₃:0.80Tb³⁺,0.015Mn²⁺ sample at different temperatures manifested that our prepared phosphors possessed good thermal stability. The luminescence properties investigation results revealed the potential value of Ba₃Lu(PO₄)₃F:Tb³⁺,Mn²⁺ in application for UV excited phosphor converted white light emitting diodes.     

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.     

Tunable Color of Eu2+/Mn2+ Coactivated Na5Ca2Al(PO4)4 via Energy Transfer

Eu²⁺ and Eu²⁺/Mn²⁺‐activated Na₅Ca₂Al(PO₄)₄ phosphors have been synthesized by the combustion method. X‐ray powder diffraction profiles, luminescence spectra, chromaticity variation, and energy transfer of Na₅Ca₂Al(PO₄)₄:Eu²⁺, Mn²⁺ were investigated as a function of the Eu²⁺ and Mn²⁺ concentrations in Na₅Ca₂Al(PO₄)₄. The Na₅Ca₂Al(PO₄)₄:Eu²⁺,Mn²⁺ phosphors can be effectively excited at wavelength ranging from 300 to 430 nm, which matches well with that for near‐ultraviolet (UV) light‐emitting diode (LED) chips. Under excitation at 354 nm, Na₅Ca₂Al(PO₄)₄:Eu²⁺,Mn²⁺ not only exhibits blue‐green emission band attributed to 4f⁶5d¹→4f⁷ of Eu²⁺ but also gives an orange emission band attributed to ⁴T₁→⁶A₁ of Mn²⁺. The emission color of the phosphor can be systematically tuned from blue‐green through white and eventually to orange by adjusting the relative content of Eu²⁺ and Mn²⁺ through the principle of energy transfer. The results indicated that Na₅Ca₂Al(PO₄)₄:Eu²⁺, Mn²⁺ may serve as a potential color‐tunable phosphor for near UV white‐light LED.     

Novel rare earth free phosphors CsMg2P3O10: Mn2+ with efficient and ultra-broadband red emission for plant growth LEDs

An efficient and ultra-broadband red phosphor CsMg₂P₃O₁₀: Mn²⁺ (CMPO: Mn²⁺) is first synthesized toward indoor plant growth LEDs. The phase purity, element composition, crystal, and local electronic structure are explored to discuss the structure and photoluminescence properties. Structure refinement and series X-ray diffractometer (XRD) results show that CMPO: Mn²⁺ is well crystallized in an orthogonal crystal system. The diffuse reflection and excitation spectra show that CMPO: Mn²⁺ has strong absorption around near ultraviolet region, assigned to the [⁶A₁ → ⁴E(⁴D), ⁴T₂(⁴D), [⁴A₁(⁴G), ⁴E(⁴G)], and ⁴T₁(⁴G)] transitions of Mn²⁺, respectively. Upon 415 nm excitation, an efficient red emission centered at 647 nm with ultra-broad full width at half-maximum (FWHM ∼ 100 nm) and high quantum efficiency (IQE ∼ 44.3 %) is observed, and because of the ultra-broad FWHM, the red emission is well accordant with the absorption spectra band of phytochrome P_R and P_FR. The optimal doping contents, lifetime as well as interaction mechanism of CMPO: Mn²⁺ are discussed in detail. Finally, the excellent thermal stability (84.5% @ 140°C) and related thermal quenching mechanism of CMPO: Mn²⁺ are discussed. The above results indicate that CMPO: Mn²⁺ phosphors have great potential for application in plant growth LEDs.