Suppression of charge imbalance via Li+-Mn4+ co-incorporated Sr2YSbO6 red phosphors for warm w-LEDs

Mn⁴⁺-activated double perovskite phosphors with composition diversity have presented excellent luminescent performances. However, the charge imbalance between Mn⁴⁺ and matrix cations would increase non-radiative recombination and reduce the structural stability. Here, novel high-efficiency stable Li⁺/Mn⁴⁺ co-incorporated Sr₂YSbO₆ red phosphors are successfully synthesized via a solid-state reaction method for warm w-LEDs, where the Li⁺ ions have the effect of charge balance for Sr₂YSbO₆:Mn⁴⁺ and reduce the non-radiative energy transfer among Mn⁴⁺ ions. It is demonstrated that the substitution of Li⁺–Mn⁴⁺ pairs for Sb⁵⁺ can enhance the bonding with low-shifted diffraction peaks and high emission intensity, and prolong the decay lifetime, compared with those of Mn⁴⁺ single-doped ones. Impressively, the thermal stability is enhanced to 89.72% from 84.61% at the original value of 303 K. Finally, a w-LED device based on the optimal phosphor Sr₂YSbO₆:0.01Mn⁴⁺/0.01Li⁺ red component exhibits a correlated color temperature of 4487 K and color rendering index of 80.2. Therefore, the incorporated Li⁺ ions serve as both charge compensator and co-activator in Mn⁴⁺-activated double perovskite phosphors with the aim of high luminescent performance and thermal stability.     

Finding an efficient far-red-emitting CaMg2La2W2O12:Mn4+ phosphor toward indoor plant cultivation LED lighting

The development of high-brightness far-red-emitting phosphors with emission wavelength within 650–750 nm is of great significance for indoor plant cultivation light-emitting diode (LED) lighting. Herein, we demonstrate a novel efficient far-red-emitting phosphors CaMg₂La₂W₂O₁₂:Mn⁴⁺ (abbreviated as CMLW:Mn⁴⁺) toward application in plant cultivation LEDs. Interestingly, the CMLW:Mn⁴⁺ phosphors show a broad excitation band in the 250–600 nm spectral range with two peaks at 352 and 479 nm, indicating they could be efficiently excited by near-ultraviolet and blue light. Under 352 nm excitation, the CMLW:Mn⁴⁺ phosphors exhibit an intense far-red emission band in the wavelength range of 650–800 nm peaking at 708 nm, corresponding to the ²E_g → ⁴A_2g transition of Mn⁴⁺ ions. Mn⁴⁺ doping concentration-dependent luminescence properties are studied in detail, and the concentration quenching mechanism is also investigated. Particularly, the internal quantum efficiency of CMLW:Mn⁴⁺ phosphors reaches as high as 44%, and their PL spectra match well with the absorption spectrum of phytochrome P_FR (P_FR stands for far-red-absorbing form of phytochrome). Furthermore, a prototype LED device is fabricated by coating the as-prepared CMLW:0.8%Mn⁴⁺ phosphors on a 460 nm blue LED chip, which produces bright far-red emissions upon 20–300 mA driving currents. This work reveals that the newly discovered far-red-emitting CMLW:Mn⁴⁺ phosphors hold great potential for application in indoor plant cultivation.     

Preparation and photoluminescence properties of Mn-activated M2Si5N8 (M=Ca, Sr, Ba) phosphors

Mn²⁺-doped M₂Si₅N₈ (M=Ca, Sr, Ba) phosphors have been prepared by a solid-state reaction method at high temperature and their photoluminescence properties were investigated. The Mn²⁺-activated M₂Si₅N₈ phosphors exhibit narrow emission bands in the wavelength range of 500-700 nm with peak center at about 599, 606 and 567 nm for M=Ca, Sr, Ba, respectively, due to the ⁴T₁(⁴G)→⁶A₁(⁶S) transition of Mn²⁺. The long-wavelength emission of Mn²⁺ ion in the host of M₂Si₅N₈ is attributed to the effect of a strong crystal-field of Mn²⁺ in the nitrogen coordination environment. Also it is observed that there exists energy transfer between M₂Si₅N₈ host lattice and activator (Mn²⁺). The potential applications of these phosphors have been pointed out.     

Optical characteristics of europium and terbium doped strontium orthogermanate phosphors

In this work, europium and terbium activated Sr₂GeO₄ phosphors were successfully developed by traditional solid state method. Powders XRD, FESEM, EDS, FTIR, DRS and PL techniques have been used to probe the as prepared phosphors. Powder XRD patterns of the phosphors are indexed. The elemental composition of phosphors was obtained from their EDS. FTIR spectra are employed to detect different vibrational groups in phosphor compositions. The DRS profiles of both pristine and Eu³⁺ (Tb³⁺) substituted samples exhibit broad and strong band in the 230–370 ​nm region. The photoluminescence studies of europium and terbium doped phosphors exhibited optimistic red emission at 617 ​nm (⁵D₀ → ⁷F₂ of Eu³⁺ ions) and intense green emission at 543 ​nm (⁵D₄ → ⁷F₅ of Tb³⁺ ions) upon ultraviolet (UV) excitations respectively. The CIE chromaticity co-ordinates are produced in deep red and green regions. Therefore, these materials may become potential alternatives for red and green phosphors in the display devices and in lamp industry.     

Luminescence and long-lasting afterglow in Mn<Superscript>2+</Superscript> and Eu<Superscript>3+</Superscript> co-doped ZnO–GeO<Subscript>2</Subscript> glasses and glass ceramics prepared by sol–gel method

To develop new fluorescent and afterglow materials, Mn²⁺ and Eu³⁺ co-doped ZnO–GeO₂ glasses and glass ceramics were prepared by a sol–gel method and their optical properties were investigated by measuring luminescence, excitation and afterglow spectra, and luminescence quantum yield (QY). Under UV irradiation at 254 nm, some glasses and all of the glass ceramics showed green luminescence peaking at 534 nm due to the ⁴T₁ → ⁶A₁ transition of tetrahedrally coordinated Mn²⁺ ions. The strongest luminescence was observed in a glass ceramic of 0.1MnO–0.3Eu₂O₃–25ZnO–75GeO₂ heat treated at 900 °C, with QY of 49.8%. All of the green-luminescent glasses and glass ceramics showed green afterglow, and the afterglow lasting for more than 60 min was obtained in a glass ceramic heat treated at 900 °C. It is considered that the Eu³⁺ ions may behave as electron trapping centers to be associated with the occurrence of the green afterglow due to the Mn²⁺ ions in the co-doped system.     

Novel high-saturated red-emitting phosphor Sr9(Mg0.5Mn0.5)K(PO4)7: Eu2+ with great quantum efficiency enhancement by La3+ codoping for white LED application

In this work, a novel whitlockite-structure red-emitting phosphor host, Sr₉(Mg_0.5Mn_0.5)K(PO₄)₇, is designed and successfully synthesized via a solid-state reaction. Upon X-ray diffractometer Rietveld refinement, it is revealed that this compound possesses compact Eu²⁺-Mn²⁺ distance (3.6809 Å) and large intra-Mn²⁺ distance (8.9905 Å), which is beneficial to the high-efficient Eu²⁺-Mn²⁺ energy transfer. By Eu²⁺ sensitization, our new phosphor exhibits a high-saturated and bright red Mn²⁺ emission at 620 nm with high color purity of 97.9%. Great emission enhancement up to 245 times than host is achieved by La³⁺ heterovalent substitution, which can be ascribed to the La³⁺-induced further structural confinement effect. Moreover, the quantum efficiency is boosted by twofold. The as-fabricated white phosphor-converted LEDs device shows bright warm white light with correlated color temperature (CCT) of 3,487 K, color-rendering index (CRI) of 92.4, and luminous efficacy of 31.59 lm/W. This work proves the feasibility of chemical unit co-substitution strategy in emission engineering of Mn²⁺-based phosphors, which can stimulate further studies on the red-emitting phosphor materials.     

Two-color emission of Zn2SiO4:Mn from ionic liquid mediated synthesis

Yellow emitting β-Zn₂SiO₄:Mn²⁺ and green emitting α-Zn₂SiO₄:Mn²⁺ nanoparticles are synthesized by nucleation applying a zinc-containing ionic liquid. As-prepared material is non-agglomerated and very uniform with a mean diameter of 32 nm. According to X-ray diffraction (XRD) two crystallographic different modifications of Zn₂SiO₄ can be realized by annealing of as-prepared and non-crystalline nanomaterial at 750 and 1000 °C. Surprisingly, these crystalline materials are still nanosized, non-agglomerated and redispersible. Scanning electron microscopy (SEM) and dynamic light scattering (DLS) confirm particle diameters of 18 nm (β-Zn₂SiO₄:Mn²⁺) and 14 nm (α-Zn₂SiO₄:Mn²⁺). Photoluminescence indicates Mn²⁺-related emission at an average wavelength of 579 nm and 528 nm, and a quantum yield of 7% and 12% for β-Zn₂SiO₄:Mn²⁺ and α-Zn₂SiO₄:Mn²⁺, respectively.     

Using an excellent near-UV-excited cyan-emitting phosphor for enhancing the color rendering index of warm-white LEDs by filling the cyan gap

White light-emitting diodes (LEDs) with high color rendering index (CRI) and low correlated color temperature (CCT) are desirable for next-generation solid-state lighting. In this work, we demonstrated an efficient near-UV-excited cyan-emitting phosphor based on Ce³⁺-doped Ca₂LuHf₂Al₃O₁₂ (CLHAO) garnet, which could be used to cover the cyan gap for fabricating high-CRI warm-white LEDs. We found that the CLHAO:Ce³⁺ samples exhibited a broad excitation band in the 300–450 nm wavelength range peaking at 400 nm, and upon 400 nm excitation they showed broad cyan emission bands in the 420–600 nm spectral region with peak positions ranging from 477 to 493 nm. The optimal CLHAO:0.02Ce³⁺ sample had CIE color coordinates of (0.160, 0.255), and its internal and external quantum efficiencies were measured to be 84.3% and 60.8%, respectively. Impressively, the luminescence intensity of CLHAO:0.02Ce³⁺ sample at 423 K still remained at 62% of the initial value at 303 K, and the chromaticity shift was calculated to be as low as 1.7 × 10^?2, revealing its high thermal stability and color stability at a higher temperature. Finally, a warm-white LED device (CCT = 3,194 K) was fabricated by combining CLHAO:0.02Ce³⁺ cyan phosphors with commercial blue/green/red tricolor phosphors, showing bright white-light emission with a high CRI of 89.4, which was superior to that of another warm-white LED device (CRI = 83.2) fabricated without CLHAO:0.02Ce³⁺ cyan phosphors. These outstanding luminescence properties of CLHAO:Ce³⁺ cyan phosphors illustrated that they offer a new feasible approach for the production of high-CRI warm-white LEDs toward high-color-quality solid-state lighting.     

Single-phased white-light emitting CaAl<Subscript>2</Subscript>Si<Subscript>2</Subscript>O<Subscript>8</Subscript>: Eu<Superscript>2+</Superscript>, Mn<Superscript>2+</Superscript> phosphors prepared by a sol–gel method

CaAl₂Si₂O₈: Eu²⁺, Mn²⁺ phosphors have been prepared by a sol–gel method. X-ray diffractometer, spectrofluorometer and UV–Vis spectrometer were used to characterize structural and optical properties of the samples. The results indicate that anorthite (CaAl₂Si₂O₈) directly crystallizes at 1000 °C in the sol–gel process. CaAl₂Si₂O₈: Eu²⁺, Mn²⁺ phosphors show two emission bands excited by ultraviolet light. Blue (around 415 nm) and yellow (around 575 nm) emissions originate from Eu²⁺ and Mn²⁺, respectively. With appropriate tuning of Mn²⁺ content, CaAl₂Si₂O₈: Eu²⁺, Mn²⁺ phosphors exhibit different hues and relative color temperatures.     

Luminescence properties of Eu- and Ce-doped CaAl2S4 and application in white LEDs

The Eu²⁺- and Ce³⁺-doped CaAl₂S₄ phosphors were comparatively synthesized by conventional solid-state reaction and the evacuated sealed quartz ampoule. The X-ray diffraction (XRD) patterns show that the sample with better crystalline quality was prepared by the evacuated sealed quartz ampoule, resulting in the enhancement of the emission intensity of Eu²⁺ ion by a factor of 1.7. The intensive green LEDs were also fabricated by combining CaAl₂S₄:Eu²⁺ with near-ultraviolet InGaN chips (λ_em=395 nm). The dependence of as-fabricated green LEDs on forward-bias currents shows that it presents good chromaticity stability and luminance saturation, indicating that CaAl₂S₄:Eu²⁺ is a promising green-emitting phosphor for a near-UV InGaN-based LED. In addition, the optical properties of CaAl₂S₄:Ce³⁺ were systematically investigated by means of diffuse reflectance, photoluminescence excitation and emission, concentrating quenching and the decay curve.     

空气中合成固溶体荧光粉Ba2(Zn, Mg)Si2O7:Ce3+,Eu2+,Eu3+及其发光特性

采用高温固相法在空气中合成了Ba_1.97-yZn_1-xMg_xSi₂O₇:0.03Eu,yCe³⁺系列荧光粉。分别采用X-射线衍射和荧光光谱对所合成荧光粉的物相和发光性质进行了表征。在紫外光330~360 nm激发下,固溶体荧光粉Ba_1.97-yZn_1-xMg_xSi₂O₇:0.03Eu的发射光谱在350~725 nm范围内呈现多谱峰发射,360和500 nm处有强的宽带发射属于Eu²⁺离子的4f⁶5d¹-4f⁷跃迁,590~725 nm红光区窄带谱源于Eu³⁺的⁵D₀-⁷F_J (J=1,2,3,4)跃迁,这表明,在空气气氛中,部分Eu³⁺在Ba_1.97-yZn_1-xMg_xSi₂O₇基质中被还原成了Eu²⁺;当x=0.1时,荧光粉Ba_1.97Zn_0.9Mg_0.1Si₂O₇:0.03Eu的绿色发光最强,表明Eu³⁺被还原成Eu²⁺离子的程度最大。当共掺入Ce³⁺离子后,形成Ba_1.97-yZn_0.9Mg_0.1Si₂O₇:0.03Eu,yCe³⁺荧光粉体系,其发光随着Ce³⁺离子浓度的增大由蓝绿区经白光区到达橙红区;发现名义组成为Ba_1.96Zn_0.9Mg_0.1Si₂O₇:0.01Ce³⁺,0.03Eu的荧光粉的色坐标为(0.323,0.311),接近理想白光,是一种有潜在应用价值的白光荧光粉。讨论了稀土离子在Ba₂Zn_0.9Mg_0.1Si₂O₇基质中的能量传递与发光机理。     

Mn4+-, Tb3+,4+-, and Er3+-activated red phosphors in the MgAl2Si2O8 system

Mn⁴⁺ doped and Tb^3+,4+, Er³⁺ co-doped MgAl₂Si₂O₈-based phosphors were prepared by conventional solid-state synthesis at 1,300 °C. They were characterized by thermogravimetry, differential thermal analysis, X-ray powder diffraction, photoluminescence, and scanning electron microscopy. The luminescence mechanism of the phosphors, which showed broad red emission bands in the range of 600–715 nm and had different maximum intensities when activated by UV illumination, was discussed. Such a red emission can be attributed to the intrinsic ²E → ⁴A₂ transitions of Mn⁴⁺.     

Color tuning by co-doping of Er doped TiO2 phosphors within a fixed Er concentration

In this paper, we report the color tuning of Er doped TiO₂ upconversion phosphors within a fixed Er concentration using 976 nm semiconductor laser diode excitation. By codoping with Mo, Yb or Li ions in the Er doped TiO₂, the green and red upconversion emissions from the ²H_11/2/⁴S_3/2 → ⁴I_15/2 and ⁴F_9/2 → ⁴I_15/2 transitions of Er ions were enhanced selectively and the color output of Er doped TiO₂ could be tuned by different intensity ratios of green to red emissions. The two-photon absorption processes were responsible for the green and red upconversion emissions of Er–Mo, Er–Yb and Er–Li codoped TiO₂ phosphors, and the corresponding enhanced mechanisms were discussed. It is expected that these color tuned phosphors within a fixed Er concentration have great potential for applications in biology, displays and other optical technology.     

Synthesis and protective properties of titanium nitride coatings on willemite

The instability of brightness and light output of a photoluminescent phosphor based on Mn²⁺-activated willemite (Zn₂SiO₄:Mn) were examined as influenced by the ultrafine titanium nitride layers synthesized based on a molecular layering technique. Using the technique of radical-recombination luminescence excited in a stream of hydrogen atoms, the spectral characteristics of the initial and of modified phosphors were determined.     

空气中合成固溶体荧光粉Ba_2(Zn,Mg)Si_2O_7∶Eu~(2+),Eu~(3+),Ce~(3+)及其发光特性

采用高温固相法在空气中合成了Ba1.97-yZn1-xMgxSi2O7∶0.03Eu,y Ce3+系列荧光粉。分别采用X-射线衍射和荧光光谱对所合成荧光粉的物相和发光性质进行了表征。在紫外光330~360 nm激发下,固溶体荧光粉Ba1.97-yZn1-xMgxSi2O7∶0.03Eu的发射光谱在350~725 nm范围内呈现多谱峰发射,360和500 nm处有强的宽带发射属于Eu2+离子的4f 65d1-4f 7跃迁,590~725 nm红光区窄带谱源于Eu3+的5D0-7FJ(J=1,2,3,4)跃迁,这表明,在空气气氛中,部分Eu3+在Ba1.97-yZn1-xMgxSi2O7基质中被还原成了Eu2+;当x=0.1时,荧光粉Ba1.97Zn0.9Mg0.1Si2O7∶0.03Eu的绿色发光最强,表明Eu3+被还原成Eu2+离子的程度最大。当共掺入Ce3+离子后,形成Ba1.97-yZn0.9Mg0.1Si2O7∶0.03Eu,y Ce3+荧光粉体系,其发光随着Ce3+离子浓度的增大由蓝绿区经白光区到达橙红区;发现名义组成为Ba1.96Zn0.9Mg0.1Si2O7∶0.03Eu,0.01Ce3+的荧光粉的色坐标为(0.323,0.311),接近理想白光,是一种有潜在应用价值的白光荧光粉。讨论了稀土离子在Ba2Zn0.9Mg0.1Si2O7基质中的能量传递与发光机理。     

Waterproof Alkyl Phosphate Coated Fluoride Phosphors for Optoelectronic Materials

A facile approach for coating red fluoride phosphors with a moisture‐resistant alkyl phosphate layer with a thickness of 50–100 nm is reported. K₂SiF₆:Mn⁴⁺ particles were prepared by co‐precipitation and then coated by esterification of P₂O₅ with alcohols (methanol, ethanol, and isopropanol). This route was adopted to encapsulate the prepared phosphors using transition‐metal ions as cross‐linkers between the alkyl phosphate moieties. The coated phosphor particles exhibited a high water tolerance and retained approximately 87 % of their initial external quantum efficiency after aging under high‐humidity (85 %) and high‐temperature (85 °C) conditions for one month. Warm white‐light‐emitting diodes that consisted of blue InGaN chips, the prepared K₂SiF₆:Mn⁴⁺ phosphors, and either yellow Y₃Al₅O₁₂:Ce³⁺ phosphors or green β‐SiAlON: Eu²⁺ phosphors showed excellent color rendition.     

Tailoring of strong orange-red-emitting materials for luminescence lifetime thermometry,anti-counterfeiting,and solid-state lighting applications

Strong orange-red-emitting Ba₂LaTaO₆:Eu³⁺ phosphors were designed and applied in various optical applications of luminescence lifetime thermometer, anti-counterfeiting film, and solid-state lighting applications. The crystal structure, elemental composition, asymmetry ratio, and other luminescent behaviors were investigated in detail. Especially, the optimal Ba₂LaTaO₆:0.1Eu³⁺ phosphor presented remarkable quantum yield (45.29%) and thermal stability (71.52% at 423 K). Based on the temperature-dependent luminescence decay curves, the maximum relative sensing sensitivity was 0.185 × 10^?2 K^?1 at 513 K. In addition, a novel anti-counterfeiting technique was introduced. The fabricated polydimethylsiloxane films exhibited three different colors under the irradiations of room light, 254 nm light, and 365 nm light, respectively. Eventually, the packaged light-emitting diode displayed the pure orange-red emission. Briefly, a series of the Eu³⁺-activated Ba₂LaTaO₆ phosphors with excellent luminescent properties were characterized and further applied in several optical fields for the first time.     

Site Occupancies,Electron–Vibration Interaction and Energy Transfer of CaMgSi2O6: Eu2+, Mn2+ Phosphors for Potential Temperature-Sensing and Anti-counterfeiting Applications

Eu²⁺-, Mn²⁺- and Eu²⁺−Mn²⁺-doped CaMgSi₂O₆ phosphors have been prepared by a high-temperature solid-state reaction. Systematic investigation of the concentration- and temperature-dependent luminescence of Mn²⁺ showed that Mn²⁺ ions occupy two distinct sites in CaMgSi₂O₆. Electron–vibration interaction (EVI) analyses of Mn²⁺ ions revealed Huang–Rhys factors of 4.73 and 2.82 as well as effective phonon energies of 313 and 383 cm⁻¹ for the two sites. Eu²⁺−Mn²⁺ energy transfer is also discussed, and its efficiency is estimated by lifetime and luminescence spectra. The different thermal quenching behaviours of Eu²⁺ and Mn²⁺, the distinct emission colours of Eu²⁺ (blue, band peak at ∼451 nm) and Mn²⁺ (yellow–red range, band peaks at ∼583 and 693 nm) endow the co-doped samples with potential applications in luminescence thermometry and temperature-/excitation wavelength-responsive dual anti-counterfeiting.     

Red luminescence in MgO-GeO<Subscript>2</Subscript> gel glasses and glass ceramics doped with Mn ions prepared by sol-gel method

To obtain red luminants, MgO-GeO₂ gel glasses and glass ceramics doped with manganese ions were prepared by a sol-gel method and their properties were investigated by measuring X-ray diffraction (XRD), electron spin resonance (ESR), and luminescence and excitation spectra. Under UV irradiation at 254 nm, the gel glasses and glass ceramics showed red luminescence at 620–665 nm, the intensity of which became strong with increasing the heat-treatment temperature. A glass ceramic with the composition 1.0MnO-25MgO-75GeO₂ heat treated at 1000°C exhibited the strongest red luminescence at 661 nm. From the results of XRD and ESR, this luminescence is found to be due to the transition from the ⁴T_1g to the ⁶A_1g state of octahedrally coordinated Mn²⁺ ions located in MgGeO₃ polycrystals. The luminescence wavelength of the glass ceramics (∼665 nm) is long compared with Eu³⁺-containing phosphors (612 nm), therefore the glass ceramics can be expected for red luminants.     

Obtain full visible spectrum light-emitting diode illumination via bismuth-activated cyan phosphors

Developing highly efficient cyan-emitting fluorescent materials is essential to bridge the cyan gap in phosphor-converted white light-emitting diodes for full-spectrum white illumination. Here, a Bi-doped cyan phosphor has been reported to solve this gap. The phase purity, photoluminescence emission/excitation spectra, concentration quenching, lifetime decay curves, and temperature-dependent photoluminescence emission spectra were systematically investigated. SrLaGaO₄:Bi³⁺ exhibits a broad excitation band (250–400 nm), which matches with the emission of a commercial near-ultraviolet light-emitting diode chip. The cyan light peaked at 475 nm is observed, which is attributed to the ³P₁→¹S₀ transition of Bi³⁺. The thermal quenching experiment was performed, and the activation energy was calculated as 0.36 eV. Finally, full-spectrum white light-emitting diode devices were fabricated using SrLaGaO₄:Bi³⁺ phosphors, commercial blue BaMgAl₁₀O₁₇:Eu²⁺ phosphor, green (Ba, Sr)₂SiO₄:Eu²⁺ phosphor, and red CaAlSiN₃:Eu²⁺ phosphor, which displayed an International Commission on an illumination coordinate of (0.3732, 0.3850), a correlated color temperature of 4290 K, and a color rendering index of 93.2 at a drive current of 20 mA. This result indicates that SrLaGaO₄:Bi³⁺ plays an essential role in bridging the cyan gap, providing new inspiration for applying cyan-emitting phosphors in full-spectrum white lighting.