Synthesis of K2SiF6:Mn4+ Phosphor from SiO2 Powders via Redox Reaction in HF/KMnO4 Solution and Their Application in Warm‐White LED

In this article, we propose a facile method for synthesis of K₂SiF₆:Mn⁴⁺ phosphor and discuss its promising application in warm‐white light emitting diodes (LED). The K₂SiF₆:Mn⁴⁺ was synthesized from SiO₂ powders through redox reaction in HF/KMnO₄ solution. The optical properties of LEDs containing different ratios of K₂SiF₆:Mn⁴⁺ phosphor and commercial Ce³⁺‐doped garnets (YAG‐40) yellow–green phosphor were studied. A warm‐white LED, with color temperature of 3510 K and color rendering index of 90.9 and efficacy of 81.56 lm/W was demonstrated.     

Key role of Nb5+ in achieving water-resistant red emission in K2Ta1-xNbxF7:Mn4+ phosphors

Mn⁴⁺-activated fluoride is one of the most important red phosphors for white light-emitting diodes (WLEDs) with high color rendering index (CRI). Due to a lack of water resistance, their potential applications are limited. Although surface coating strategies improve the waterproof stability of fluoride red phosphors, they have downsides. It was found that Nb⁵⁺ plays an important role in improving the water resistance of Mn⁴⁺-activated oxyfluorides by preventing the hydrolysis of [MnF₆]^2-. In this work, the influence of Nb⁵⁺ on the waterproof stability of Mn⁴⁺-activated fluorides was explored. A set of synthesized K₂Ta_1-xNb_xF₇:Mn⁴⁺ phosphors exhibit tunable and superior water resistance. The photoluminescence (PL) intensity of the representative sample K₂Ta_0.6Nb_0.4F₇:5%Mn⁴⁺ remains nearly 100% of its initial value even after being immersed in water for 60 min, which is significantly higher than the commercial K₂SiF₆:Mn⁴⁺ red phosphor (8.7%). Our findings open up new possibilities for the development of waterproof fluoride red 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.     

Optimized photoluminescence of red phosphor Na2SnF6:Mn4+ as red phosphor in the application in “warm” white LEDs

The Mn⁴⁺ activated fluostannate Na₂SnF₆ red phosphor was synthesized from starting materials metallic tin shots, NaF, and K₂MnF₆ in HF solution at room temperature by a two‐step method. The formation mechanism responsible for preparing Na₂SnF₆:Mn⁴⁺ (NSF:Mn) has been investigated. The influences of synthetic parameters: such as concentrations of HF and K₂MnF₆ in reaction system, reaction time, and temperature on crystallinity, microstructure, and luminescence intensity of NSF:Mn have been investigated based on detailed experimental results. The actual doping concentration of Mn⁴⁺ in the NSF:Mn host lattice is less than 0.12 mol%. The most of K₂MnF₆ is decomposed in HF solution especially in hydrothermal system at elevated temperatures. The color of the as‐prepared NSF:Mn samples changes from orange to white when the temperature is higher than 120°C, which indicates the lower concentration of luminescence centers in the crystals. A series of “warm” white light‐emitting diodes with color rendering index (CRI) higher than 88 and correlated color temperatures between 3146 and 5172 K were obtained by encapsulating the as‐prepared red phosphors NSF:Mn with yellow one Y₃Al₅O₁₂:Ce³⁺ (YAG:Ce) on 450 nm blue InGaN chips. The advantage of the synthetic strategy to obtain NSF:Mn can be extended to developing Mn⁴⁺‐doped red phosphors from low‐costing metals at room temperature for large‐scale industrial applications.     

Hydrophobic surface modification toward highly stable K2SiF6:Mn4+ phosphor for white light-emitting diodes

K₂SiF₆:Mn⁴⁺ phosphor is well known for its excellent red emission performance which is vital for improving the color rendering of white light-emitting diodes. However, the poor moisture resistance limits its application in optical devices. In this paper, K₂SiF₆:Mn⁴⁺ phosphor is coated with an inorganic hydrophobic protective layer to obtain good moisture resistance. Chemical vapor deposition method was used to decompose acetylene at high temperature, and the generated nanoscale carbon layer worked as a hydrophobic protective coating on the surface of the phosphor. Microstructure, compositions and properties of the synthesized K₂SiF₆:Mn⁴⁺@C phosphor were investigated in detail. It is found that most of the deposited carbon is coated on the surface of phosphor crystals in amorphous state. The carbon atoms are bonded with the fluorine element in K₂SiF₆:Mn⁴⁺ phosphor, forming carbon-fluorine (C–F) covalent bonds. The moisture resistance of K₂SiF₆:Mn⁴⁺@C phosphor is improved owing to the protection of the hydrophobic carbon. The relative emission intensity of K₂SiF₆:Mn⁴⁺@C phosphor could maintain 73% of the initial luminous intensity after immersing in the aqueous solution at room temperature for 8 h, whereas K₂SiF₆:Mn⁴⁺ phosphor without carbon coating was only 0.7% remaining of the initial value under the same conditions.     

LED-pumped intense red luminescence based on Ba2LaTaO6: Mn4+ double perovskite phosphor

Non-rare earth Mn⁴⁺ ion-doped red oxide phosphors have great potential for applications in warm white light-emitting diodes (wLEDs) due to their low cost and stable physicochemical properties. Herein, a series of Ba₂LaTaO₆ (BLTO): Mn⁴⁺ phosphors were successfully synthesized by the high-temperature solid-state method. The theoretical values of the band gap calculated by the density functional theory are close to the experimental values obtained by the absorption spectroscopy. In addition, the phosphors have a broad excitation band in the wavelength range of 280–550 nm and emit red light at the peak wavelength of 681 nm under excitation. The concentration quenching of the BLTO: Mn⁴⁺ phosphor was caused by dipole-dipole interactions. The activation energy and the average decay lifetimes of the samples were calculated. Meanwhile, the effects of synthesis temperature and Li⁺ ion doping on the luminescence performance of the samples were also investigated. Satisfactorily, the color purity and internal quantum efficiency of the phosphor reached 98.3% and 26.8%, respectively. Further, the samples were prepared as red-light components for warm wLEDs. The correlated color temperature, color rendering index, and luminous efficiency of the representative devices driven by 60 mA current were 5190 K, 83.3, and 81.59 lm/W, respectively. This work shows that the BLTO: Mn⁴⁺ red phosphor with excellent luminescence performance can be well applied to warm wLEDs.     

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.     

A low sintering temperature glass based on SiO2–P2O5–ZnO–B2O3–R2O system for white LEDs with high color rendering index

A low sintering temperature glass based on the SiO₂–P₂O₅–ZnO–B₂O₃–R₂O (R=K and Na) system was studied as a matrix for embedding phosphors to fabricate color tunable white LEDs. The proposed system, which uses no heavy‐metal elements and can be sintered at 500°C, incorporates thermally weak commercial phosphors such as CaAlSiN₃:Eu²⁺ to produce phosphor‐in‐glasses (PiGs). Changing the mixing ratio of glass to phosphors affected the photo‐luminescence spectra and color coordinates of the PiGs when mounted on a blue LED. The color rendering index (CRI) and color correlated temperature (CCT) of the LEDs were also varied with the mixing ratio, providing color tunable white LEDs. A high CRI, up to 93, as well as highly improved thermal stability were obtained, along with a low sintering temperature compared to other glass systems, suggesting the practical feasibility of the proposed system.     

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⁺.     

Sr-induced color-tunable and thermal stability enhancing in the phosphor (Ba1-xSrx)9Lu2Si6O24:Eu2+ for solid-state lighting

Rare earth ions’ site occupation is significant for studying luminescence properties by changing the host composition. The (Ba_1-xSr_x)₉Lu₂Si₆O₂₄:Eu²⁺ (x = 0-0.4) tunable-color phosphors were synthesized via a high temperature solid-state reaction. With the Sr²⁺ ions concentration increase, the luminescent color could be tuned from blue to green. This phenomenon is discussed in detail through the ions occupation in the host lattice. More importantly, the temperature-dependent luminescence of (Ba_1-xSr_x)₉Lu₂Si₆O₂₄:Eu²⁺ phosphors was investigated and exhibited excellent thermal stability. Furthermore, white LED device has been fabricated using (Ba_1-xSr_x)₉Lu₂Si₆O₂₄:Eu²⁺ phosphor mixed with commercial red phosphor Sr₂Si₅N₈:Eu³⁺ combined with a 370 nm UV-chip. This device showed correlated color temperature (CCT) of 5125 K and high color render index (CRI) of 91. This phosphor will be a promising candidate as a tunable-color phosphor for UV-based white LEDs.     

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.     

Insight into a novel rare-earth-free red-emitting phosphor Li3Mg2NbO6:Mn4+: Structure and luminescence properties

Red phosphor is indispensable to achieve warm white light in the white light diode (WLED) application. However, the current red phosphors suffer from high cost and harsh synthesis conditions. In this study, an oxide-based rare-earth-free red-emitting phosphor Li₃Mg₂NbO₆:Mn⁴⁺ (LMN:Mn⁴⁺) has been successfully synthesized by a simple solid-state reaction method. The relationship between crystal structure and luminescence was investigated in detail. The site occupancy of the doping Mn⁴⁺ ion in the LMN host has been discussed from the point of bond valence sum. How the coordination environment of doping Mn⁴⁺ affects the energy level of doping Mn⁴⁺ ion has been illustrated via the Tanabe-Sugano energy-level diagram. Moreover, warm white light has been obtained using LMN:Mn⁴⁺ as compensator to the YAG:Ce³⁺.     

HF-free molten salt route for synthesis of highly efficient and water-resistant K2SiF6:Mn4+ for warm white LED

It has been one of the hot issues to prepare the red-emitting Mn⁴⁺-doped fluoride phosphors with highly efficient and waterproofness for warm white-light-emitting diodes (WLEDs) by the green and environmentally friendly method. Herein, we design a novel green molten salt route to synthesize K₂SiF₆:Mn⁴⁺ red powder using molten NH₄HF₂ salt instead of HF liquor as the reaction medium. The results show that KMnO₄ and MnF₂ could produce Mn⁴⁺ in NH₄HF₂ molten salt through a reduction reaction, and the resulting Mn⁴⁺-doped K₂SiF₆ exhibited a bright red emission peaked at 632 nm under blue light excitation. The luminescence intensity of the as-obtained product after immersing into water for 24 hours maintain nearly 100% of that before soaking and emission peak shape remains unchanged. The thermal stability of the sample was evaluated by temperature-dependent luminescence spectral intensity during heating and cooling. Furthermore, a warm white-light-emitting diodes (WLEDs) with an excellent color rendering index (Ra = 87.1), lower correlated color temperature (CCT = 3536K), and high luminous efficacy (116.99 lm·W⁻¹) was fabricated based on blue chip and K₂SiF₆:Mn⁴⁺ and commercial yellow phosphor (Y₃Al₅O₁₂:Ce³⁺).     

Improvement of the luminescent thermal stability and water resistance of K2SiF6:Mn4+ by surface passivation

Mn⁴⁺-doped fluoride phosphors can solve the problem for lack of red emitting component in commercial white light-emitting diodes (WLEDs). However, its application is seriously hindered by its easy hydrolysis. Here, we propose to use sodium sulfite as a passivator to treat K₂SiF₆:Mn⁴⁺. After passivation, a Mn⁴⁺-rare K₂SiF₆ protective layer can be formed in situ on the surface of the phosphor, and lead to improved emission intensity, luminescent thermal stability and moisture resistance. When soaking in water for 6 h, the integrated fluorescent intensity of the passivated sample maintained 90.8% of the initial value, while the intensity of the un-passivated sample sharply decreased to 10.2% of the initial value. Mechanisms to improve the emission, water resistance and thermal stability of the luminescence are proposed and discussed. WLED was assembled with the passivated sample, and good performance of warm white light (CCT = 2963 K, Ra = 90.4) was obtained.     

An efficient far-red emission Sr2InSbO6:Mn4+, M (M = Li+, Na+, and K+) phosphors for plant cultivation LEDs

High-efficiency and far-red light phosphors based on Mn⁴⁺-doped inorganic luminescence materials are beneficial to plant cultivation. However, Mn⁴⁺-doped oxide phosphors have a common problem of low quantum efficiency. Alkali metal ion codoping can effectively improve the luminescence properties of Mn⁴⁺-activated oxide phosphors. Herein, a series of Sr₂InSbO₆:Mn⁴⁺, M (SISO:Mn⁴⁺, M) (M = Li⁺, Na⁺, and K⁺) far-red-emitting phosphors codoped alkali metal ions were first synthesized. Density functional theory calculation indicated that SISO is a kind of indirect bandgap material with a bandgap of ∼1.60 eV. The SISO:Mn⁴⁺ samples showed a far-red light at 698 nm upon 365 nm, which perfectly matched the absorption spectrum of the far-red-phytochrome (Pfr) of plants. The doping concentration of the SISO:Mn⁴⁺ samples was optimized to be 0.006 mol. The concentration quenching mechanism was defined as dipole–dipole interaction by combining the Dexter theory and the Inokuti–Hirayama model. Optimizing the sintering temperature and codoped with alkali metal ions (Li⁺, Na⁺, and K⁺) could improve the luminescent intensity of SISO:Mn⁴⁺. The optimum sintering temperature was 1300°C. The internal quantum efficiencies of SISO:0.006Mn⁴⁺ and SISO:0.006Mn⁴⁺, 0.006Li⁺ phosphors are 22.67% and 60.56%, respectively. SISO:Mn⁴⁺, Li⁺ phosphors-based plant growth light-emitting diodes (LEDs) demonstrate excellent optical stability and long lifetime. Thus, these phosphors are promising candidates for plant cultivation LEDs.     

Preparation and optical properties of a novel double-perovskite phosphor,Ba2GdNbO6:Mn4+, for light-emitting diodes

Red phosphors serve an important function as red components of warm white light-emitting diodes (WLEDs). Given their remarkable luminescent properties and low cost, Mn⁴⁺-doped phosphors are attracting significant attention. In this study, the novel red phosphor Ba₂GdNbO₆:Mn⁴⁺ was synthesized through high-temperature solid-state reaction. The host Ba₂GdNbO₆ with a double-perovskite structure was investigated. Scanning electron microscopy and thermogravimetric analysis were performed to evaluate the structure and thermal stability of the phosphor, respectively. PLE and photoluminescence spectra were further used to study the luminescence properties of the phosphor. Moreover, crystal field strength and Racah parameters were calculated to estimate the nephelauxetic effect of Mn⁴⁺ on the Ba₂GdNbO₆ host lattice. Thermal quenching characteristics were also analyzed. The fabricated red-emitting LED revealed its potential application in WLEDs.     

A novel Mn4+‐activated red phosphor for use in light emitting diodes,K3SiF7:Mn4+

Phosphors that exhibit a narrow red emission are particularly interesting due to the advantage of providing a more extensive color gamut and better rendering in LED applications such as displays and solid‐state lighting. Although some Eu²⁺‐activated nitridosilicates have been discovered in this regard, K₂SiF₆:Mn⁴⁺ phosphors are the only option in actual LED applications thus far. We discovered a novel phosphor, K₃SiF₇:Mn⁴⁺, with P4/mbm symmetry. The luminescent properties of K₃SiF₇:Mn⁴⁺ are almost identical to those of the K₂SiF₆:Mn⁴⁺ phosphor, but its materials identity is distinct due to a completely different crystallographic structure, which leads to reduced decay time. The fast decay is one of the most serious disadvantages of existing K₂SiF₆:Mn⁴⁺ phosphors. The K₃SiF₇:Mn⁴⁺ phosphor was examined in comparison to the K₂SiF₆:Mn⁴⁺ via density functional theory calculation, Rietveld refinement, X‐ray photoelectron spectroscopy, X‐ray absorption near‐edge structure spectroscopy, and time‐resolved photoluminescence.     

Zero-thermal-quenching of LiAl5O8: Eu2+, Mn2+ phosphors by energy transfer and defects engineering

The photoluminescence behavior of inorganic phosphors is generally influenced by thermal stability, which determines the luminescence efficiency of the corresponding devices. Here, a series of Eu²⁺, Mn²⁺ co-doped LiAl₅O₈ blue-green-emitting phosphors with thermal robust are successfully fabricated. The concentration-dependent emission spectra and the decay curves of the as-obtained LiAl₅O₈: Eu²⁺, Mn²⁺ samples manifest the occurrence of the energy transfer from Eu²⁺ to Mn²⁺ ions via dipole-dipole interaction, and the corresponding emitted colors are gradually modulated from blue to green under the excitation of 310 nm. Moreover, the zero-thermal-quenching luminescence is observed when the operation temperature is up to 423 K, which is attributed to the energy release from the trapping centers to emitting centers (Eu²⁺ and Mn²⁺) at high temperature. Furthermore, a warm white light-emitting diodes (WLEDs) device with correlated color temperature of 5061 K, a color rendering index of 80.6 and long-term stability is fabricated by combining UV LED chip (λ_ex = 310 nm), as-obtained LiAl₅O₈: Eu²⁺, Mn²⁺ phosphor, commercially available red phosphor and green phosphor. These results prove the potential application of the as-obtained LiAl₅O₈: Eu²⁺, Mn²⁺ phosphor for UV-pumped WLEDs devices.     

A universal HF-free synthetic method to highly efficient narrow-band red-emitting A2XF6:Mn4+ (A = K,Na, Rb,Cs; X = Si,Ge, Ti) phosphors

Mn⁴⁺-activated fluoride red-emitting narrow-band phosphors have been successfully used in wide color-gamut white LEDs for liquid crystal display (LCD) backlights. However, highly concentrated and toxic HF is usually used in their synthesis, causing environment and safety issues. In this work, we proposed a HF-free green method, that is, using NH₄F/HCl instead of HF, to synthesize a series of A₂XF₆:Mn⁴⁺ (A = K, Na, Rb, Cs; X = Si, Ge, Ti) phosphors. The microstructure, photoluminescence (PL) properties, thermal quenching, and applications of the synthesized phosphors were investigated. Using the proposed approach, the phosphors generally showed a pure phase, a particle size ranging from 5 to 45 μm, and some characteristic sharp emission lines of Mn⁴⁺ in the red spectral range. The internal quantum efficiency was varied in a broad range of 69%-94% under the 460 nm excitation, depending on the composition of the fluoride host. Among these compositions, K₂XF₆:Mn⁴⁺ (X = Ge and Ti) phosphors even had a similar external quantum efficiency (>60%) with commercial ones. By combining K₂GeF₆:Mn⁴⁺ (narrow-band red) and β-sialon:Eu²⁺ (narrow-band green) with a blue LED, a white light-emitting diode (wLED) backlight with a color gamut of 87.7% National Television System Committee Standard, color temperature of 8423 K, and a luminous efficacy of 110.8 lm/W was demonstrated. These results indicate that the synthetic method proposed in this work is universal for preparing highly efficient fluoride phosphors used in wLEDs.     

Structure analysis,tuning photoluminescence and enhancing thermal stability on Mn4+-doped La2-xYxMgTiO6 red phosphor for agricultural lighting

Currently, phosphor-converted LEDs (pc-LEDs) are revolutionizing the industry of plant growth lighting. To meet the requirements of this technology, phosphors with tunable photoluminescence, high thermal stability and luminous intensity are required. Herein, we found that the simple substitution of yttrium for lanthanum in La₂MgTiO₆:Mn⁴⁺ (LMT:Mn⁴⁺) system could satisfy above three criteria simultaneously. The photoluminescence properties can be regulated by continuously controlling the chemical composition of La_2-xY_xMgTiO₆:Mn⁴⁺ solid solution. The La sites are occupied by Y ions, causing a significant blue shift in the emission spectra which owing to the change of local crystal field strengthen. Meanwhile, the thermal stability and decay lifetimes are also varied due to the variation of local structure and band gap energy. The thermal stability of the material reaches 83.5% at 150 °C, which is better than the reported La₂MgTiO₆:Mn⁴⁺ and Y₂MgTiO₆:Mn⁴⁺ phosphors. The electronic luminescence (EL) of pc-LED devices using La_2-xY_xMgTiO₆:Mn⁴⁺ red phosphor is evaluated, which matching the absorption regions of plant pigments well, reflecting the superiority of the studied phosphors in plant growth lighting areas.