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.     

Bi3+/Mn4+ co-doped dual-emission phosphors for potential plant lighting

Developing environment-friendly dual-emission phosphors of both blue–cyan and deep-red lights is desirable for the utilized indoor plant lighting research. Notably, the naked 6s and 6p Bi³⁺ ions are sensitive to the lattice sites, which emit from Ultraviolet (UV) to red lights in various crystal compounds. Meanwhile, the ²E → ⁴A_2g transition of Mn⁴⁺ ions promises its deep-red light emissions, which satisfies the demand for specific wavelength lights for plants growth. Hence, a Bi³⁺/Mn⁴⁺ co-doped Sr₂LaGaO₅: Bi³⁺, Mn⁴⁺ (SLGO:Bi³⁺:Mn⁴⁺) phosphor was finally synthesized. The phase, micromorphology and luminescent properties were systematically evaluated. Upon excitation at 350 nm light, dual emissions of both blue–cyan (470 nm) and deep-red (718 nm) lights were observed. Besides, due to the pronounced photoluminescence (PL) spectral overlap between Bi³⁺ and Mn⁴⁺ ions, a potential energy transfer process from Bi³⁺ to Mn⁴⁺ ions was confirmed. The relative PL intensities between Bi³⁺ and Mn⁴⁺ ions can be tuned just by adjusting the Mn⁴⁺ ion concentration. Besides, Li⁺ co-doping has been evidenced to improve the deep-red emissions (718 nm) of SLGO:0.005Mn⁴⁺ due to charge compensation and rationally designed lattice distortion, together with the improved thermal stability. Finally, the emissions of SLGO:Bi³⁺, Mn⁴⁺, Li⁺ phosphor suit properly with the absorption of the four fundamental pigments for plant growth, indicating that the prepared phosphorescent materials may have a prospect in plant light-emitting diodes lighting.     

Toward temperature-dependent Bi3+-related tunable emission in the YVO4:Bi3+ phosphor

Up until now, many previous works have indicated us that the photoluminescence (PL) properties of phosphors sometimes can be changed with the change in the external temperature, resulting in the anomalous PL phenomena and correlated new applications that are difficult to achieve at room temperature. In this work, we report the temperature-dependent Bi³⁺-related PL properties in the YVO₄:Bi³⁺ phosphor. Our findings show that increasing the temperature from 10 to 300 K enables manipulating the energy interaction from groups to Bi³⁺, thereby leading to the temperature-induced color tuning from blue (0.183, 0.212) to yellow (0.418, 0.490). Upon this heating process, we further reveal that the dynamic Bi³⁺ luminescence has experienced a regular transition from double-exponential to single-exponential decay, which results in the decrease in the average Bi³⁺ lifetime from 122.606 to 0.376 μs. Discussions on the PL results imply that the tunable PL observations are due to the interplay of temperature-dependent energy transfer from groups to Bi³⁺ and redistribution of the excited ³P₀ and ³P₁ states of Bi³⁺ upon the thermal stimulation. This work not only presents the temperature-triggered Bi³⁺ tunable properties in the well-studied YVO₄ host lattice but also can provide new insights into revealing Bi³⁺-related PL mechanism in other Bi³⁺-doped photonic materials in the future and, in the meanwhile, gives some directive ideas for us to explore previously unnoticed applications for rare-earth (RE; eg, Eu³⁺, Pr³⁺, Tb³⁺, Eu²⁺, Er³⁺, etc) and other non-RE (eg, Bi³⁺, Mn⁴⁺, Mn²⁺, Cr³⁺, etc) doped phosphors.     

溶剂热法合成片状SrAl2O4:Eu2+,Dy3+长余辉荧光粉的研究

利用溶剂热法制备了由片组装的花状前驱体,1300℃烧结2h后获得了SrAl2O4:Eu2+,Dy3+片状荧光材料.利用XRD和SEM技术表征了在不同比例的乙醇和水的混合溶液中反应制得的荧光材料的物相组成和形貌,用荧光分光光度计测定了荧光材料的发光性质.结果发现,当乙醇和水的比例为3∶1时,所制备的荧光材料具有较高的结晶性,较好的形貌和较强的发光强度.     

Insight into luminescent properties,energy transfer and thermal stability of NaBa4(AlB4O9)2Cl3:Ce3+, Tb3+ phosphors

A series of Ce³⁺ and Tb³⁺ singly- and co-doped NaBa₄(AlB₄O₉)₂Cl₃ (NBAC) phosphors have been synthesized via high-temperature solid state route. The crystal structure, morphology, photoluminescent properties, thermal properties and energy transfer process between Ce³⁺ and Tb³⁺ were systematically investigated. The structure refinements indicated that the phosphors based on NBAC crystallized in P42nm polar space group in monoclinic phase. The emission color could be tuned from blue (0.1595, 0.0955) to green (0.2689, 0.4334) via changing the ratio of Ce³⁺/Tb³⁺. The energy transfer mechanism of Ce³⁺/Tb³⁺ was verified to be dipole–quadrupole interaction via the examination of decay times of Ce³⁺ based on Dexter's theory. The good thermal stability showed the intensities of Ce³⁺ at 150°C were about 66.9% and 64.88% in NBAC:0.09Ce³⁺ and NBAC:0.09Ce³⁺, 0.07Tb³⁺ of that at room temperature, and the emission intensities of Tb³⁺ remained 102.41% in NBAC:0.11Tb³⁺ and 95.22% in NBAC:0.09Ce³⁺, 0.07Tb³⁺ due to the nephelauxetic shielding effect and the highly asymmetric rigid framework structure of NBAC. The maximum external quantum efficiency (EQE) of Ce³⁺ in NBAC:0.09Ce³⁺, yTb³⁺ phosphors could reach 43.38% at y = 0.13. Overall, all the results obtained suggested that NBAC:Ce³⁺, Tb³⁺ could be a promising option for n-UV pumped phosphors.     

Efficient red and broadband near-infrared luminescence in Mn2+/Yb3+-doped phosphate phosphor

In this work, we report a novel phosphor LSPO:Mn²⁺ that exhibits red emission at about 616 nm and pleasant broad near-infrared (NIR) emission at about 800 nm with a full width at half maximum (fwhm) of 112 nm. The structure and spectra show that the doped manganese ions occupy two kinds of Sc sites forming Mn1 and Mn2 emission centers, which are responsible for red and NIR emission, respectively. The XPS and low-temperature fluorescence spectra reveal that both red and NIR emissions come from the Mn²⁺ ions. Besides, NIR luminescence is improved by doping Yb³⁺ in LSPO:Mn²⁺, leading to the broadened NIR emission range (700-1100 nm) and enhanced luminescent thermal stability. Our results suggest that the prepared LSPO:Mn²⁺ and LSPO:Mn²⁺,Yb³⁺ phosphors offer the potential applications as red and NIR components in phosphor-converted white-light-emitting diodes (pc-WLED) and broadband NIR pc-LED. Meanwhile, this work provides a new way to design novel broadband NIR phosphors.     

燃烧法合成SrAl2O4:Eu2+,Dy3+发光材料及其性能研究

采用燃烧法在较低温度下快速合成了SrAlO:Eu2 ,Dy3 长余辉发光粉体,并利用XRD、荧光分光光度24计等测试手段,研究了合成粉体的物相结构以及工艺因素对材料发光性能的影响。结果表明,发光粉体的主晶相为SrAlO,属单斜晶系,晶胞参数为a=0.8442nm,b=0.8827nm,c=0.5162nm,β=97°;激发光谱主峰波长为24398nm、349nm、324nm,发射光谱主峰波长为516nm。     

NaY(WO4)2:Dy3+荧光粉的制备及其上转换发光性能

利用水热法合成了NaY(WO4)2:Dy3+上转换荧光粉. 通过XRD、SEM表征该荧光粉结构和形貌. 探讨了Dy3+浓度、pH值、反应温度及焙烧温度对NaY(WO4)2:Dy3+晶体结构、形貌及发光性能的影响,得到在Dy3+浓度为0.5%,pH=8,反应温度180℃,800℃焙烧条件下的样品具有最佳上转换发光性能. 利用776 nm近红外光激发NaY(WO4)2:Dy3+,观察到480 nm处的蓝光发射峰以及577 nm处的黄光发射峰. 其中蓝光来自Dy3+离子的4F9/2→6H15/2跃迁,黄光由Dy3+离子4F9/2→6H13/2跃迁产生.     

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⁺.     

Visible emission and energy transfer in Tb3+/Dy3+ co-doped phosphate glasses

In this work, we systematically study the spectroscopic properties of Tb³⁺/Dy³⁺ co-doped phosphate glasses in the visible spectral region and explore the sensitization role of Dy³⁺ in the enhancement of visible fluorescence of Tb³⁺ ions. Judd-Ofelt parameters Ω₂ and Ω₄/Ω₆ of the phosphate glass as host for Tb³⁺ are calculated as 21.60 × 10^-20 cm² and 0.73, respectively, based on the measured spectral absorption. Multiple energy transfer (ET) routes from Dy³⁺ to Tb³⁺ and their efficiencies are characterized, and the enhanced fluorescence properties of Tb³⁺ are investigated, including the emission spectral strength and the spontaneous emission lifetime as functions of Dy³⁺ doping concentration. The efficient nonradiative ET processes between Dy³⁺ and Tb³⁺ allow a moderate concentration level of Tb³⁺ to achieve favorably stronger spectral absorption at blue and ultraviolet wavelengths. Tb³⁺/Dy³⁺ co-doped phosphate glass shows promising potential for phosphors and lasing operation at visible wavelengths.     

水热法合成SrAl2O4:Eu2+,Dy3+长余辉材料

研究了SrAl2O4：Eu^2 ，Dy^3 长余辉材料的一种新合成方法。首先利用水热法制备出该发光材料的前驱体，然后将此前驱体粉体在还原气氛下高温烧结，得亮度高，余辉时间长的洲SrAl2O4：Eu^2 ，Dy^3 超细长余辉材料，并对其发光性能进行了研究。并对水热法和复合沉淀法合成的此种材料进行了比较。     

掺铽的铝酸锶铕镝磷光体的发光特性及晶相分析

采用高温固相法在弱还原气氛下制备了掺入Tb3 的SrAl2O4:Eu2 ,Dy3 磷光体.研究了Tb3 对SrAl2O4:Eu2 ,Dy3 磷光体的发光性能的影响.结果发现,引入Tb3 以后,对基质SrAl2O4的晶体结构基本上没有影响,也未改变磷光体的发光光谱,却使磷光体的初始亮度显著提高,并使余辉时间延长.其余辉强度随时间的变化由最初的快衰减过程和随后的慢衰减过程组成,符合t-1.1的双曲线规律.并初步探讨了Tb3 的作用机制.     

Luminescent properties of long‐lasting BaAlxOy:Eu2+,Dy3+ nanocomposites

BaAl_xO_y:Eu²⁺,Dy³⁺ blue‐green phosphor samples were synthesized by a combustion method at the low temperature of 500°C. Phosphor nanocrystallites with high brightness were obtained without significantly changing the crystalline structure of the host. The crystallite sizes determined from the Scherrer equation ranged between 34 and 41 nm. Different volume fractions of the BaAl_xO_y:Eu²⁺,Dy³⁺ powder were then introduced in LDPE polymer. The resulting composites were similarly analyzed and also thermally characterized by means of differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). PL results indicate that the LDPE‐phosphor interface, which is considered to have an influence on the composite behavior, did not significantly change the spectral positions of the phosphor materials, whose major emission peaks occurred at about 505 nm. The improved afterglow results for the composites may have been caused by morphological changes due to increased surface area and defects. Thermal results indicate that the BaAl_xO_y:Eu²⁺,Dy³⁺ particles acted as nucleating centers and enhanced the overall crystallinity in the LDPE nanocomposite while preventing lamellar growth, hence reducing the crystallite sizes in LDPE. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

New apatite-type phosphor Ca9La(PO4)5(SiO4)F2:Tb3+,Dy3+ with improved color rendering index

Ca₉La(PO₄)₅(SiO₄)F₂:Tb³⁺,Dy³⁺ (CLPSF:Tb³⁺,Dy³⁺) phosphors were successfully prepared using the traditional solid-state technique. The crystal structure was refined and the luminescence properties have been examined in detail. The band gap and electronic structure of Ca₉La(PO₄)₅(SiO₄)F₂ were performed by the periodic density functional theory (DFT) calculation. The spectral and fluorescence decay dynamics of CLPSF:Tb³⁺,Dy³⁺ show that the energy transfer behavior between Tb³⁺ and Dy³⁺ ions is observed. The CLPSF:Tb³⁺,Dy³⁺ phosphors can be efficiently excitable at the wavelengths range from 300 to 500 nm. The emission spectrum covers the whole visible part of the spectra with the sharp emission bands in red, green, and blue regions. The correlated color temperature (CCT) and color rendering index (CRI) of white light emission could be improved by the fine-tuning of the Tb³⁺ and Dy³⁺ ions ration in accordance with the energy transfer behavior. Thus, the CLPSF:Tb³⁺,Dy³⁺ phosphor could be used as a material for the near-ultraviolet (n-UV) and white light-emitting diodes (w-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.     

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.     

Broadband deep-red-to-near-infrared emission from Mn2+ in strong crystal-field of nitride MgAlSiN3

Broadband near-infrared (NIR) phosphors have received increasing attention for fabricating phosphor-converted light-emitting diodes (pc-LEDs) as NIR light source. Most of the reported broadband NIR phosphors originate from Cr³⁺ in weak crystal field environments. Herein, we report a luminescent material, MgAlSiN₃:Mn²⁺ with CaAlSiN₃-type structure, demonstrating that broadband deep-red-to-NIR emission can be achieved via doping Mn²⁺ into crystallographic sites with strong crystal field in inorganic solids. This phosphor is synthesized via easy-handle solid-state reaction, and the optimized sample, (Mg_0.93Mn_0.07) AlSiN₃ shows an emission band with peak at ~754 nm, FWHM of 150 nm, and internal quantum efficiency of 70.1%. The photoluminescence intensity can further be enhanced by co-doping Eu²⁺ as sensitizer. This work provides a new strategy for discovering new broadband NIR phosphors using Mn²⁺ in strong crystal field as luminescence center.     

掺钆的铝酸锶铕镝磷光体的发光特性及晶相分析

采用高温固相法在弱还原气氛下制备了掺入Gd3+的SrAl2O4:Eu2+,Dy3+磷光体.研究了Gd3+对SrAl2O4:Eu2+,Dy3+磷光体的发光性能的影响.结果发现:引入Gd3+以后,对SrAl2O4基质的晶体结构基本上没有影响,也并未改变磷光体的发光光谱,却使磷光体的初始亮度显著提高,并使余辉时间延长.其余辉强度随时间的变化由最初的快衰减过程和随后的慢衰减过程组成,符合t-1.1的双曲线规律.并初步探讨了Gd3+的作用机制.     

The effect of Dy3+ doping on the thermoluminescence properties of Ba2SiO4

The thermoluminescence (TL) properties of barium silicate phosphor, Ba₂SiO₄:%3Dy³⁺ synthesized by using hydrothermal method were investigated and presented in detail. The crystallographic structure of Ba₂SiO₄:%3Dy³⁺ was determined by conventional x-ray diffraction technique and the results showed that the sample was grown in orthorhombic phase with Pmcn (62) space group (PDF: 01-077-0150). The excitation spectra of Ba₂SiO₄:Dy³⁺ were measured in the wavelength range of 220-400 nm and the spectra showed that there were several excitation bands in the sample. The CIE chromaticity coordinates were also calculated from emission spectra for Dy³⁺-doped Ba₂SiO₄. In order to calculate the kinetic parameters of the sample the additive dose, peak shape and computerized glow curve deconvolution methods were used. It was found that Ba₂SiO₄:Dy³⁺ was composed of five general order TL glow peaks. The fading characteristics of the sample were also studied over a period time. At the end of the planned storage times, the normalized TL peak area of Ba₂SiO₄:Dy³⁺ reduced 60% of its original value.     

Novel double-perovskite Mg2InSbO6:Sm3+ phosphor with excellent heat-resistant performance and high color purity used in white LEDs

In this study, Sm³⁺-doped double-perovskite Mg₂InSbO₆ phosphors were synthesized via high-temperature solid-state reaction. Mg₂InSbO₆ belongs to the double-perovskite family with a space group of R (No.148). The photoluminescence (PL) spectrum illustrates that Mg₂InSbO₆:0.05Sm³⁺ phosphor can emit intense orange-red emission light at 607 nm due to the ⁴G_5/2→⁶H_7/2 transition. The optimum concentration of Mg₂InSbO₆:xSm³⁺ is confirmed to 0.05 mol. The asymmetric ratio (⁴G_5/2→⁶H_9/2/⁴G_5/2→⁶H_5/2) of Mg₂InSbO₆:0.05Sm³⁺ phosphor is 2.73. The quenching temperature exceeds 500 K, illustrating that Mg₂InSbO₆:Sm³⁺ sample has excellent heat resistance. The high color purity and correlated color temperature (CCT) of Mg₂InSbO₆:Sm³⁺ phosphors are obtained. Furthermore, a white light-emitting diode (w-LED) is successfully fabricated, possessing CCT of 6769 K and high color rendering index (R_a) of 89. Therefore, the orange-red-emitting Mg₂InSbO₆:Sm³⁺ phosphors exhibit great potential to apply in solid-state lighting fields.