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.     

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⁺.     

Host sensitization of Mn4+ in self‐activated Na2WO2F4:Mn4+

Self‐activated compound serving as host sensitizer for trivalent rare‐earth ions has been intensively studied, but only in more recent years did it extend to non‐rare‐earth ions. In the present work, it is demonstrated for the first time that the parity‐forbidden Mn⁴⁺ red emission can be effectively enhanced by utilizing the strong parity‐allowed absorption of O^2?–W⁶⁺ charge transfer band and the energy transfer from “WO₂” groups to Mn⁴⁺ ions. Hopefully, the presently studied self‐activated Na₂WO₂F₄ can be developed as stable color converter for field‐emission displays.     

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.     

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.     

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.     

Tuning Mn4+ Red Photoluminescence in (K,Rb)2Ge4O9:Mn4+ Solid Solutions by Partial Alkali Substitution

We report on intense photoluminescence from materials of the (Rb,K)₂Ge₄O₉:Mn⁴⁺ solid solution as a novel class of red‐emitting oxide phosphors. In these compounds, luminescence originates from a virtually ideal substitution of Mn⁴⁺ for Ge⁴⁺ on octahedral lattice sites which are well‐isolated from each other within the unit cell by intermediate GeO₄ species. Complete isostructural substitution of K for Rb is possible across the join. The associated slight shrinkage of the unit cell has only little effect on the apparent Mn⁴⁺ interionic distance, but enables tuning of the absorption cross section and of the band structure, hence, of the emission lifetime, of the excitation band shape, and of emission quantum yield. Partial substitution was also found to reduce thermal quenching of the Mn⁴⁺‐related emission, apparently due to the lower polarizability of the K⁺ ion. In addition, random substitution of Rb by K enables modulation of the interaction of Mn⁴⁺ with its surrounding field at lower symmetry, leading to increasing emission bandwidth, i.e., 595 cm^?1 in K_1.5Rb_0.5Ge₄O₉:Mn⁴⁺ vs 558 or 578 cm^?1 in Rb₂Ge₄O₉:Mn⁴⁺ or K₂Ge₄O₉:Mn⁴⁺ respectively.     

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.     

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.     

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.     

A Facile Route to BaSiF6:Mn4+ Phosphor with Intense Red Emission and Its Humidity Stability

Red phosphor BaSiF₆:Mn⁴⁺ has been synthesized by a hydrothermal method at 120°C for 24 h, in which either Si or SiO₂ is used as silicon source. HF as weak acid performs a complex agent for the formation of anion groups [SiF₆]^2? and [MnF₆]^2?. The luminescence properties of undoped BaSiF₆ have been firstly observed. The dependence of luminescence intensities of BaSiF₆:Mn⁴⁺ on the concentrations of HF and KMnO₄ in precursory solution has been investigated. The as‐prepared BaSiF₆:Mn⁴⁺ exhibits high chemical stability even in deionized water.     

Exploration of bluish violet-emitting phosphor Ca3Al4ZnO10:Ti4+ with enhanced emission by Ca2+ vacancies

In this paper, we introduced a bluish violet-emitting phosphor Ca₃Al₄ZnO₁₀:Ti (IV) (CAZO:Ti⁴⁺) synthesized by high-temperature solid-state reaction. Upon 265 nm excitation, a broad emission band spanned from 300 nm to 500 nm and centered at 370 nm was observed. In addition, the effects of flux and charge compensation to photoluminescence properties of CAZO:Ti⁴⁺ were systematically investigated. The results show that 103% improvement of emission intensity was achieved when 1% H₃BO₃ flux was introduced and 32.8% enhancement of it for 2% Ca²⁺ vacancies doped as charge compensator. Moreover, the lifetimes, band gap energy, concentration quenching mechanism, as well as electron transition process of CAZO:Ti⁴⁺ were discussed. Due to the efficient broad bluish violet emission, this phosphor may find a potential application in mercury vapor-excited fluorescent lamp for plant growth.     

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

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

Dual-activator luminescence of LuAG:Mn4+/Tb3+ phosphor for optical thermometry

Mn⁴⁺ and Tb³⁺ singly doped and Mn⁴⁺/Tb³⁺ codoped lutetium aluminum garnet (Lu₃Al₅O₁₂, or simply LuAG) phosphors were synthesized and investigated for the application of optical thermometry. X-ray powder diffraction and luminescence spectroscopy measurements were performed on all samples to analyze their crystal phases and optical properties. In particular, temperature-dependent luminescence of the LuAG:Mn⁴⁺/Tb³⁺ sample was measured at the temperature range of 270–420 K. The results showed that the luminescence intensity of Mn⁴⁺ has gone through a remarkable decline while the luminescence of Tb³⁺ has an only insignificant change with the rise of temperature which leads to a dramatic decrease in the fluorescence intensity ratio (FIR) between the two activator Mn⁴⁺ and Tb³⁺. Further analysis showed that the LuAG:Mn⁴⁺/Tb³⁺ sample used for temperature sensing has a high relative sensitivity with maximum value of 4.3% K⁻¹ at 333 K. Our research indicated that this LuAG:Mn⁴⁺/Tb³⁺ material is a promising candidate for FIR-type optical temperature sensing.     

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.     

Design of a defect-induced orange persistent luminescence phosphor BaZnGeO4:Bi3+

We report a novel bright orange persistent luminescence (PersL) phosphor BaZnGeO₄:Bi³⁺ with broad emission and PersL spectra. Its crystal structure, photoluminescence (PL) spectra, thermoluminescence (TL) spectra and PersL spectra were investigated in detail. The two emission bands at 440 nm and 595 nm originate from Bi³⁺ ions in normal Ba²⁺ sites (Bi1) and Ba²⁺ sites close to vacancy defects (Bi2), respectively. The introduction of and defects improves the emission intensity of Bi2 more than that of Bi1, demonstrating that Bi2 is related to the vacancy defects. The orange emission and PersL properties of BZGO:Bi³⁺ can be improved when a little and defects are introduced, because the introduction of and defects makes it easier for Bi³⁺ to enter in Ba²⁺ sites; and for PersL, and defects can perform as the effective trap centers to capture more charges, which is beneficial for PersL. BZGO:Bi³⁺ has quite good thermal stability, and the bright orange PersL can be observed by the naked eye for 1 h. Finally, a feasible PersL mechanism of BZGO:Bi³⁺ was proposed to clarify the PersL-generation process.     

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.     

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.     

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

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

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.