High luminescent thermal stability and water resistance of K2SiF6:Mn4+@CaF2 red emitting phosphor

K₂SiF₆:Mn⁴⁺ (KSF:Mn⁴⁺), as an efficient red-emitting phosphor, has a promising application in WLEDs (white light-emitting diodes). However, poor moisture resistance performance still hinders its deeper commercialization. Here, KSF:Mn⁴⁺@ CaF₂ with high water resistance and luminescent thermal stability has been prepared though H₂O₂-free hydrothermal method and surface coating process. Both KSF:Mn⁴⁺ and KSF:Mn⁴⁺@CaF₂ all have high luminescent thermal stability, due to negative thermal quenching (NTQ) effect. Mechanism of the NTQ has been discussed and suggested as thermal-light energy conversion mechanism. Compared with KSF:Mn⁴⁺, water resistance of KSF:Mn⁴⁺@CaF₂ is greatly improved by coating of CaF₂, because the outer shell of CaF₂ can effectively prevent the [MnF₆]^2- group on the surface of the phosphor from being hydrolyzed into MnO₂. The results of water resistance test shows that after immersing in water for 360 min (6 h), luminescent intensity of the uncoated product drops to 41.68% of the initial one, while that of the coated product remains to have 88.24% of its initial one. Warm white light with good luminescent performances (CCT = 3956 K and Ra = 89.3) is got from prototype WLEDs assembled by using the optimal coated sample. The results suggest that the optimal coated sample has potential application in blue-based warm WLEDs.     

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.     

Silica nanoparticles assisted preparation of reddish-yellow emitting Eu2+ activated remote-type CaSrSiO4 phosphor for warm white LED applications

A reddish-yellow emitting silicate-based remote phosphor has been developed via the wet-solid phase reaction technique. By employing silica nanoparticles (200 nm), Eu²⁺ doped CaSrSiO₄ phosphor was developed and its efficacy has been examined thoroughly. The developed remote phosphor can get excited over a broad region of the spectrum ranging from ultraviolet to blue (250–500 nm) and as generates a reddish-yellow emission peaked at 580 nm covering a broad range of spectral components (450–800 nm) with a quantum efficiency of 52%. The thermoluminescence studies of developed remote phosphor exhibit 50% of the stable emission up to 200 °C without any shift in the emission wavelength. The developed remote phosphor was then utilized for the making of a proto-type LED using 450 nm blue-emitting commercial LED. The output emission from the proto-type LED confirms the production of efficient warm white light with CCT <5000 K and CRI >85.     

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.     

Development of red-emitting Ba2LaSbO6:Mn4+ phosphors for latent fingerprint detection

Latent fingerprints provide crucial affirmations of identity in forensic science. However, they are microscopic. In this study, novel fluorescence materials, Ba₂LaSbO₆:Mn⁴⁺ (BLSO:Mn⁴⁺) phosphors, were developed by a sol–gel method for the fluorescence imaging of latent fingerprints. The structural properties of the phosphors were investigated by powder X-ray diffraction (XRD) and its Rietveld refinement analyses, and transmission electron microscopy and scanning electron microscopy techniques. The photoluminescence properties of the BLSO:Mn⁴⁺ phosphors were evaluated comprehensively by recording the emission, excitation, and decay curves. The BLSO:Mn⁴⁺ phosphors provide a high-intensity red emission at 677 nm under 350 nm excitation caused by the ²E_g→⁴A_2g transition of Mn⁴⁺. The optimum concentration of Mn⁴⁺ in the BLSO host was determined to be ~0.2 mol%. The calculated Commission International de L'Eclairage (CIE) chromaticity coordinates (0.716, 0.283) of the emission from the BLSO:Mn⁴⁺ phosphor are located in the pure red region of the CIE 1931 diagram. The red-emitting BLSO:0.2Mn⁴⁺ phosphor was used as a fluorescence imaging powder for visualizing latent fingerprints on various substrates with high resolution, high contrast, and high efficiency, as well as good selectivity.     

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.     

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.     

Soluble silica assisted synthesis and luminescent characteristics of yellow emitting CaSrSiO4:Eu2+ phosphors for warm white light production

To meet the challenges and additional requirements towards the development of white LED׳s with utmost efficacy, a sol–gel approach is adopted wherein a water soluble silicon compound is used as a silica source. The phosphor material obtained is subjected to detailed structural, morphological and luminescent studies. The results obtained show that the XRD patterns of Eu²⁺ doped CaSrSiO₄ phosphors are in good agreement with the CaSrSiO₄ (ICSD no. 49660) whose structure is orthorhombic. The output of the luminescence studies clearly portrays a broad yellow emission between 450 and 750 nm with a peak at ~600 nm under the broad excitation range. This confirms its efficient emission towards the development of a warm white light using blue LEDs. A red shift in the peak emission wavelength was observed for the prepared samples. This longer shift in wavelength can be credited to the sol–gel method adopted and is not offered by the conventional solid state reaction method. A warm white emitting LED was fabricated by combining near ultraviolet LED (400 nm) chip with our sol–gel synthesized CaSrSiO₄:Eu²⁺ phosphor. The CIE chromaticity coordinates (0.44 and 0.41), color correlated temperature (CCT) <4000 K, color rendering index (CRI) >80 provide their emission potentiality in the warm white light region.     

Bismuth-activated,narrow-band,cyan garnet phosphor Ca3Y2Ge3O12:Bi3+ for near-ultraviolet-pumped white LED application

Herein, a novel Bi³⁺-activated Ca₃Y₂Ge₃O₁₂ (CYGO) narrow-band cyan-emitting phosphor was synthesized. It can be excited from 320–420 nm, and the strongest excitation peak is located at 370 nm, which is suitable for current near-ultraviolet (NUV) chips perfectly. The full width at half maximum is at 52 nm. By analyzing the crystal structure of the sample, we infer that the Bi³⁺ ions replace the Y³⁺ site to form a highly symmetrical BiO₆ octahedron. The time-resolved photoluminescence (TRPL) spectra of CYGO: Bi³⁺ reveal that the only a single emission center exists in the host lattice. A warm white light–emitting diode (WLED) device with a low correlated color temperature (3148 K) and a high color rendering index (90.2) was fabricated by using the as-prepared sample, and the significant thermal stability of CYGO: Bi³⁺ guarantees its potential application in WLEDs. It is verified that the structure with only one crystallographic Y site for Bi³⁺ dopant occupation and highly symmetrical and dense structure is conducive to realize narrow-band emission, which will provide experience for researchers to explore more Bi³⁺-activated phosphors used for high-end lighting.     

A single-source molten salt synthesis of rod-shaped Na2Ti6O13 crystals

As one of the most potential negative electrode materials, Na₂Ti₆O₁₃ is expected to play an important role in the area of high-performance battery. In this work, we have developed an easy, efficient and controllable method to prepare rod-shaped Na₂Ti₆O₁₃ crystals. This approach utilized a single-source molten salt strategy and only needed to sinter a special precursor synthesized from an aqueous solution containing H₃BO₃ and (NH₄)₂TiF₆ in presence of sodium salts. The component and shape of precursor crystals can be tuned by adjusting the reagent concentration and reaction temperature. By sintering precursor crystals in air at 900 °C for 30 min, Na₂Ti₆O₁₃ with high crystallinity and purity can be obtained. X-ray diffraction and scanning electron micrographs results of different sintering times show that the sintering process can be divided into two steps. Firstly, the precursor crystals are converted to TiO₂ (anatase) nano-particles and amorphous sodium salts. Subsequently, molten salt reaction occurs between amorphous sodium salts and TiO₂ and forms rod-shaped Na₂Ti₆O₁₃ crystals.     

Facile synthesis of the desired red phosphor Li2Ca2Mg2Si2N6:Eu2+ for high CRI white LEDs and plant growth LED device

The red emission with suitable peak wavelength and narrow band is acutely required for high color rendering index (CRI) white LEDs without at the cost of the luminous efficacy. Herein, the Li₂Ca₂Mg₂Si₂N₆:Eu²⁺ red phosphor was prepared with facile solid-state method using Ca₃N₂, Mg₃N₂, Si₃N₄, Li₃N, and Eu₂O₃ as the safety raw materials under atmospheric pressure for the first time, which shows red emission peaking at 638 nm with full width at half maximum (FWHM) of 62 nm under blue light irradiation and becomes the desired red phosphor to realize the balance between luminous efficacy and high CRI in white LEDs. The morphology, structure, luminescence properties, thermal quenching behavior, and chromaticity stability of the Li₂Ca₂Mg₂Si₂N₆:Eu²⁺ phosphor are investigated in detail. Concentration quenching occurs when the Eu²⁺ content exceeds 1.0 mol%, whereas high-temperature photoluminescent measurements show a 32% drop from the room-temperature efficiency at 423 K. In view of the excellent luminescence performances of Li₂Ca₂Mg₂Si₂N₆:Eu²⁺ phosphor, a white LEDs with CRI of 91 as a proof-of-concept experiment was fabricated by coating the title phosphor with Y₃Al₅O₁₂:Ce³⁺ on a blue LED chip. In addition, the potential application of the title phosphor in plant growth LED device was also demonstrated. All the results indicate that Li₂Ca₂Mg₂Si₂N₆:Eu²⁺ is a promising red-emitting phosphor for blue LED-based high CRI white LEDs and plant growth lighting sources.     

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.     

Novel color tunable LaCaGaO4:Bi3+,Eu3+ phosphors for high color rendering warm white LEDs

A series of LaCaGaO₄:xBi³⁺,yEu³⁺ (x = 0.002–0.04, y = 0.02–0.45) phosphors with adjustable emission colors were synthesized by high-temperature solid-state reaction. The samples were identified as pure phases by X-ray diffraction and Rietveld refinement, and the crystal structures were analyzed in detail. The LaCaGaO₄:xBi³⁺ phosphor shows an intense blue emission under near-ultraviolet excitation, originating from the ³P₁ → ¹S₀ transition. The spectrum analysis reveals that the Bi³⁺ ions occupy two luminescence centers in the LaCaGaO₄ host and that energy transfer can occur. A model of the energy transfer between the Bi³⁺ and Eu³⁺ ions was also created and studied in detail. As the Eu³⁺-concentration increased, the emission color of the LaCaGaO₄:0.005Bi³⁺,yEu³⁺ phosphor changed from blue to pink to red. In addition, the fluorescence lifetime, quantum yield, thermal stability, and other properties of the phosphors were characterized and analyzed. Finally, two white light-emitting diode devices with R_a values of 96.6 and 95 and correlated color temperatures of 4578 and 3324 K were fabricated, indicating the potential of phosphors for warm white lighting applications.     

Solution growth of millimeter-scale Na2SiF6 single crystals for Mn4+-doping as red phosphor

The cation exchange method has been demonstrated to be efficient in doping Mn⁴⁺ ions into various fluorides to synthesize the red-emitting LED phosphors. This paper, however, reports the challenge in using this method to dope Mn⁴⁺ into the Na₂SiF₆ single crystals, to prepare the fluoride phosphor in single-crystal form, a state-of-the-art study in the white LED lighting field. The millimeter-sized Na₂SiF₆ single crystals with a uniform columnar morphology (2–3 mm in length) were successfully grown in solution by a slow cooling process after optimizing the precursors. Then, the crystals were soaked in the HF solution dissolved with K₂MnF₆ to implement Mn⁴⁺-doping via the cation exchange process. Evaluation of the Mn⁴⁺-doping behavior reveals that the Mn⁴⁺ ↔ Si⁴⁺ cation exchange is less efficient in the case of single crystal host compared with the polycrystalline powdery ones and by-reactions also occur which generates new phases. The Na₂SiF₆ single crystals doped with Mn⁴⁺ exhibit a series of discrete sharp peaks with intense zero phonon line emission at 617 nm under 450 nm blue irradiation. This study may trigger the exploration of new single crystal fluoride phosphor.     

Zwitterionic-type molten salt: An efficient mild organocatalyst for synthesis of 2-amidoalkyl and 2-carbamatoalkyl naphthols

A green, general, and efficient method has been developed for the synthesis of 2-amidoalkyl and 2-carbamatoalkyl naphthol derivatives through a one-pot three-component condensation of 2-naphthol, aldehydes and amide or carbamates in the presence of zwitterionic-type molten salt as mild organocatalyst under solvent-free conditions.     

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.     

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.     

Controllable hydrothermal synthesis and photoluminescence properties of CaGd2(WO4)4:Eu3+ red-emitting phosphor

CaGd₂(WO₄)₄:Eu³⁺ phosphors with controllable morphology were synthesized via the hydrothermal method. The influences of pH value, reaction time and Eu³⁺ concentration on the crystal structure, morphology, and photoluminescence properties of CaGd₂(WO₄)₄:Eu³⁺ were studied. The pure tetragonal structure CaGd₂(WO₄)₄ is obtained when the pH value is 8 and 9. Furthermore, by altering the pH value of the reaction solution, the morphologies of the CaGd₂(WO₄)₄:Eu³⁺ phosphors evolve from spindle-shaped grains to tetragonal plate-like grains and finally to aggregated bulk particles. Under the 394 nm excitation, the phosphors display a bright red emission corresponding to the characteristic 4f-4f transitions of Eu³⁺, and the intensity of emission peaks depends mainly on the pH value, the reaction time, and the Eu³⁺ concentration. The optimum photoluminescence performance is achieved for CaGd_2-x(WO₄)₄:xEu³⁺ (x = 1) phosphor synthesized at pH = 8 under the reaction time of 16 h. Finally, the thermal stability of the phosphors is analyzed at different ambient temperatures.