Properties of red-emitting phosphors Sr_2MgSi_2O_7:Eu^(3+) prepared by gel-combustion method assisted by microwave

Novel red-emitting phosphors Sr2MgSi2O7：Eu3＋ were prepared by gel-combustion method assisted by microwave. The phase struc-ture and luminescent properties of as-synthesized phosphors were investigated by XRD and fluorescence spectrophotometer, respectively. The results showed that the as-synthesized sample was Sr2MgSi2O7 with tetragonal crystal structure. The excitation spectrum of Sr2MgSi2O7：Eu3＋ was composed of two major parts： one was the broad band between 200 and 350 nm, which belonged to the charge transfer of Eu3＋-O2-; the other consisted of a series of sharp lines between 350 and 450 nm, ascribed to the f-f transition of Eu3＋. The emission spec-trum consisted of two emission peaks at 593 and 616 nm, which was attributed to 5D0→7F1 and 5D0→7F2 of Eu3＋, respectively. The concen-tration of Eu3＋ （x） had great effect on the emission intensity of Sr2-xMgSi2O7：Eu3＋x. When x varied in the range of 0.04-0.18, the intensity of emission peaks at 593 and 616 nm increased gradually with the concentration of Eu3＋ increasing. It was interesting that no concentration quenching occurred. Moreover, the luminescent intensity could be greatly enhanced with incorporation of charge compensator Li＋ ions.

A potential red-emitting phosphors scheelite-like triple molybdates LiKGd_2(MoO_4)_4:Eu^(3+) for white light emitting diode applications

A series of novel red-emitting phosphors scheelite-like triple molybdates LiKGd2.xEux（MoO4）4（0.1≤ x ≤ 1.9） were synthesized by solid state reaction method and their photoluminescence properties were investigated. The photoluminescence results show that all samples can be excited efficiently by UV （396 nm） light and blue （466 nm） light and emit red （615 nm） light with line spectra, which are coupled well with the characteristic emission from UV-LED and blue LED, respectively. The experimental results and their analysis suggest that the energy transfer occurs due to dipole-dipole interactions among Eu3＋ ions in LiKGd2-xEux（MoO4）4. Compared with Cao.8MoO4： Eu0.2^3-, the emission intensity of LiKGdo.9（MoO4）4： Eu1.1^3- is about 1.4 times higher and the CIE chromaticity coordinates are as close to the National Television System Committee （NTSC） standard values as those of Cao.8MoO4： Eu0.2^3-. The optical properties suggest that LiKGdo.9（MoO4）4： Eu1.1^3- is an efficient red-emitting phosphor for white LEDs applications.

CsBaB_(3)O_(6):Eu^(3+) red-emitting phosphors for white LED and FED:Crystal structure,electronic structure and luminescent properties

Recently,borate compounds have received much attention in the field of rare earth doped phosphors due to their excellent luminescent performance.In this work,to explore the potential in LED and FED applications,the CsBaB_(3)O_(6):Eu^(3+)phosphor was investigated in detail by using Rietveld refinement,DFT calculations,photoluminescent and cathodoluminescent spectra.As a result,CsBaB_(3)O_(6)has a planar stacked three-dimensional layered structure.Under the excitation of 395 nm n-UV light and electron beam,CsBaB_(3)O_(6):Eu^(3+)phosphor exhibits a typical red emission of Eu^(3+).A good thermal stability and good resistance to saturation and degradation were observed in the CsBaB_(3)O_(6):Eu^(3+)phosphor.The related photoluminescent and cathodoluminescent mechanisms were studied.The results indicate that CsBaB_(3)O_(6):Eu^(3+)phosphor has potential in multifunctional applications.

Synthesis,crystal structure and photoluminescence properties of novel double perovskite La2CaSnO6:Eu3+red-emitting phosphors

A series of new double perovskite LaEuCaSnO(0≤x≤0.8)red phosphors were synthesized by traditional solid-state reaction.The phase,micro structure,photoluminescence(PL)properties,quantum efficiency,and thermal stability of the phosphors were investigated.LaCaSnOmatrix has a monoclinic double perovskite structure with space group P2/n.Under near-ultraviolet(UV)light at395 nm,LaEuCaSnOphosphors exhibit the most typical red emission peak at 614 nm,which corresponds to~5 D→~7 Felectric dipole transition of Eu.The optimum Eudoping content is attained at x=0.5,and the LaEuCaSnOphosphor shows a moderate quantum efficiency(32.3%)and high color purity(92.2%).Besides,the temperature-dependent spectrum of the phosphor was studied.The emission intensity of Euat 423 K decreases to 70.94%of the initial intensity at 303 K,and the activation energyΔE is estimated to be 0.232 eV,suggesting that the phosphors possess good thermal stability.The fabricated w-LED based on the phosphors has higher Ra(89),lower CCT(4539 K),and better chromaticity coo rdinates(0.371,0.428).These results prove that the Eu-doped LaCaSnOred phosphor has great potential applications in w-LEDs.

Photoluminescence properties and thermal stability of Eu^(3+)-activated La_(7)Ta_(3)W_(4)O_(30) red-emitting phosphors for near-UV-excited w-LEDs

Novel trivalent europium(Eu^(3+))-activated La_(7)Ta_(3)W_(4)O_(30):xEu^(3+)(x=0.5 mol%-40 mol%) red-emitting phosphors were synthesized by means of a high-temperature solid-state reaction.The structure,morphology,photoluminescence,thermal-stability properties,lifetime,and color-rendering of the prepared phosphors were investigated in detail.The La_(7)Ta_(3)W_(4)O_(30):Eu^(3+) phosphors show five emission peaks under near-ultraviolet(n-UV) at 397 nm,and these peaks are ascribed to the transitions of ^(5)D0-^(7)Fj(j=0,1,2,3 and 4) by Eu^(3+) ions.The optimal doping concentration of Eu^(3+) is 20 mol%,and the critical distance of the energy transfer between the Eu^(3+)ions was calculated to be 1.768 nm.The quenching temperature(T_(0.5)) of La_(7)Ta_(3)W_(4)O_(30):20 mol%Eu^(3+) is about 440 K.The quantum yield(QY) was measured to be 85.85%.The fabricated white-light-emitting diodes(w-LEDs) possess high color-rendering index(R_(a)) of 90,and high correlated color temperature(CCT) of 5810 K,respectively.The Commission Internationale de L’Eclairage(CIE) coordinates are(0.311,0.322).Therefore,the prepared phosphor has a promising application for w-LEDs.

Potential red-emitting phosphor GdNbO_4:Eu^(3+),Bi^(3+) for near-UV white light emitting diodes

A red-emitting phosphor GdNbO4：Eu3＋,Bi3＋ was prepared by a high temperature solid-state reaction technique. The phosphor was characterized by X-ray diffraction （XRD）, particle size analyzer and fluorescence spectrometer. The single phase of GdNbO4：Eu3＋,Bi3＋ was obtained at 1150~C and the average particle diameter was about 2.30 μm. Excitation and emission spectra reveal that the phosphor can be ef- ficiently excited by ultraviolet （UV） light （394 nm） and emit the strong red light of 612 nm due to the Eu3＋ transition of SD0~TF2. The opti- mum content of Eu3＋ doped in the phosphor GdNbOn：Eu3＋ is 20mo1%. The phosphor Gdo.80NbO4：0.20Eu3＋,0.03Bi3＋ shows much stronger photoluminescence intensity and better chromaticity coordinates （x=0.642, 0.352） than GdNbO4：Eu3＋. It is confirmed that Gdo.80NbO4：0.20Eu3＋,0.03Bi3＋ is a potential candidate for near-UV chip-based white light emitting diodes.

Achieving Narrowed Bandgaps and Blue-Light Excitability in Zero-Dimensional Hybrid Metal Halide Phosphors via Introducing Cation-Cation Bonding

Zero-dimensional(0D)hybrid metal halides,which consist of organic cations and isolated inorganic metal halide anions,have emerged as phosphors with efficient broadband emissions.However,these materials generally have too wide bandgaps and thus cannot be excited by blue light,which hinders their applications for efficient white light-emitting diodes(WLEDs).The key to achieving a blue-light-excitable 0D hybrid metal halide phosphor is to reduce the fundamental bandgap by rational chemical design.In this work,we report two designed hybrid copper(I)iodides,(Ph_(3)MeP)_(2)Cu_(4)I_(6)and(Cy_(3)MeP)_(2)Cu_(4)I_(6),as blue-light-excitable yellow phosphors with ultrabroadband emission.In these compounds,the[Cu_(4)I_(6)]^(2-)anion forms an I6 octahedron centered on a cationic Cu_(4)tetrahedron.The strong cation-cation bonding within the unique cationic Cu_(4)tetrahedra enables significantly lowered conduction band minimums and thus narrowed bandgaps,as compared to other reported hybrid copper(I)iodides.The ultrabroadband emission is attributed to the coexistence of free and self-trapped excitons.The WLED using the[Cu_(4)I_(6)]^(2-)anion-based single phosphor shows warm white light emission,with a high luminous efficiency of 65 Im W^(-1)and a high color rendering index of 88.This work provides strategies to design narrow-bandgap 0D hybrid metal halides and presents two first examples of blue-light-excitable 0D hybrid metal halide phosphors for efficient WLEDs.

Achieving broadband near-infrared luminescence in Cr^(3+)-Activated Y_(2)Mg_(2)Al_(2)Si_(2)O_(12)phosphors via multi-site occupancy

Cr^(3+)-activated near-infrared(NIR)phosphors are key for NIR phosphor-converted light emitting diodes(NIR pc-LED).While,the site occupancy of Cr^(3+)is one of the debates that have plagued researchers.Herein,Y2Mg2Al2-Si_(2)O1_(2)(YMAS)with multiple cationic sites is chosen as host of Cr^(3+)to synthesize YMAS:xCr^(3+)phosphors.In YMAS,Cr^(3+)ions occupy simultaneously Al/SiO4 tetrahedral,Mg/AlO6 octahedral,and Y/MgO8 dodecahedral sites which form three luminescent centers named as Cr1,Cr2,and Cr3,respectively.Cr1 and Cr2 relate to an intermediate crystal field,with transitions of^(2)E→^(4)A_(2)and^(4)T_(2)→^(4)A_(2)occurring simultaneously.As Cr^(3+)concentration increases,the^(4)T_(2)→^(4)A_(2)transition becomes more pronounced in Cr1 and Cr2,resulting in a red-shift and broadband emission.Cr3 consistently behaves a weak crystal field and exhibits the broad and long-wavelength emission.Wide-range NIR emission centering at 745 nm is realized in YMAS:0.03Cr^(3+)phosphor.This phosphor has high internal quantum efficiency(IQE?86%)and satisfying luminescence thermal stability(I423 K?70.2%).Using this phosphor,NIR pc-LEDs with 56.6 mW@320 mA optical output power is packaged and applied.Present study not only demonstrates the Cr^(3+)multi-site occupancy in a certain oxide but also provides a reliable approach via choosing a host with diverse cationic sites and local environments for Cr^(3+)to achieve broadband NIR phosphors.

Fabrication of YAG:Ce^(3+) and YAG:Ce^(3+),Sc^(3+) Phosphors by Spark Plasma Sintering Technique

In this study,a single-doped phosphors yttrium aluminum garnet(Y_(3)Al_(5)O_(12),YAG):Ce^(3+),single-doped YAG:Sc^(3+),and double-doped phosphors YAG:Ce^(3+),Sc^(3+) were prepared by spark plasma sintering(SPS)(lower than 1 200℃).The characteristics of synthesized phosphors were determined using scanning electron microscopy(SEM),X-ray diffraction(XRD),and fluorescence spectroscopy.During SPS,the lattice structure of YAG was maintained by the added Ce^(3+) and Sc^(3+).The emission wavelength of YAG:Ce^(3+) prepared from SPS(425-700 nm) was wider compared to that of YAG:Ce^(3+) prepared from high-temperature solid-state reaction(HSSR)(500-700 nm).The incorporation of low-dose Sc^(3+) in YAG:Ce^(3+) moved the emission peak towards the short wavelength.

Synthesis and Luminescence Improvement of CaAlSiN_(3) Phosphors Doped with Eu^(2+) and Mn^(2+) for White LEDs

Eu^(2+) and Mn^(2+) co-activated CaAlSiN_(3) red phosphors were produced using the solid-state reaction tech⁃nique in a N2 environment.Excitation spectra,emission spectra,and diffuse reflection spectra were used to study the luminescence characteristics,energy gap,and thermal stability in detail.CaAlSiN_(3)∶Eu^(2+) exhibits an extended emission band when stimulated with 450 nm blue light,which is caused by the 4f65d to 4f7 transition of Eu^(2+).Similar⁃ly,CaAlSiN_(3)∶Mn^(2+) displays a wide emission band centered at 628 nm,which results from Mn^(2+)’s transition from 4T1(4G) to 6A1(6S).When the ions of Mn^(2+)were combined into CaAlSiN_(3)∶Eu^(2+),the photoluminescence intensity of Eu^(2+ )was greatly boosted because there was energy transfer and co-emission between Mn^(2+) and Eu^(2+).Beyond that,CaAlSiN_(3)∶Eu^(2+),Mn^(2+) emerges with splendid thermostability and high quantum efficiency,the quenching temperature surpasses 300℃,and the internal quantum efficiency is determined to be around 84.9%.The white LED was pack⁃aged with a combination of CaAlSiN_(3)∶Eu^(2+),Mn^(2+),LuAG∶Ce3+ and a blue chip.At a warm white-light corresponding color temperature(3009 K) with CIE coordinates(0.4223,0.3748),the color rendering index Ra has reached 93.2.CaAlSiN_(3)∶Eu^(2+),Mn^(2+) would have great application potential as a red-emitting phosphor for white LEDs.

Influence of Al^(3+) doping on the energy levels and thermal property of the 3.5MgO·0.5MgF_2·GeO_2:Mn^(4+) red-emitting phosphor

A series of Al3+-doped 3.5MgO·0.5MgF2·GeO2:Mn4+red-emitting phosphors is synthesized by high temperature solid-state reaction. The broad excitation band at 300 nm–380 nm, resulting from the4A2→4T1transition of Mn4+,exhibits a blue shift with the increase of Al2O3 content. The observation of the decreased Mn4+–O2-distance is explained by the crystal field theory. The temperature-dependent photoluminescence spectra with various amounts of Al2O3 content are comparatively measured and the calculation shows that the activation energy increases up to 0.41 eV at the Al2O3 content of 0.1 mol. The maximum phonon densities of state for these samples are calculated from Raman spectra and they are correlated with the thermal properties.

Synthesis, Composition Optimization, and VUV Photoluminescence Characterization of (Y,Gd)(V,P)O_4∶Eu^(3+) as A Potential Red-Emitting Plasma-Display Panel Phosphor

The synthesis, composition optimization, VUV Photoluminescence (PL) spectra, and optical properties, of (Y,Gd)(V,P)O4∶Eu3+ phosphors were investigated by synchrotron radiation. The VUV PLE spectra and the correlation among VUV PL intensity, λem, and Eu3+, Gd3+, and P-content were established. The PLE spectral studies showed that (Y,Gd)(V,P)O4∶Eu3+ exhibited significant absorption in the VUV range. The VUV PL intensity was found to enhance with PO43- and Gd3+-doping. Furthermore, the chromaticity characteristics of (Y,Gd)(V,P)O4∶Eu3+ were also found to be (0.6614, 0.3286) and compared against (Y, Gd)BO3∶Eu3+ as a reference. Based on the characterization results, we are currently improving and evaluating the potential application of (Y,Gd)(V,P)O4∶Eu3+ as a new red-emitting PDP phosphor.

YAG∶Ce Phosphors for WLED via Nano-Pesudoboehmite Sol-Gel Route

The sub-micron sized YAG ： Ce phosphors were synthesized via a modified sol-gel method by peptizing nano-pesudoboehmite particulate. It is found that YAG phase from the dried gel powders appears at 1000 ℃ then the pure YAG phase exists at a relatively lower sintering temperature of 1400 ℃. The smaller sizes of phosphors in the ranges of 1 - 3 μm are obtained due to the contribution of seeding effects of nano-sized alumina particles to strengthen each step of the processes. Both the excitation and emission spectra of photoluminescence of the phosphor obtained at 1400 ℃ meet well with the spectroscopic requirements of the WLED phosphors.

Investigations on Valence-Change Behaviors of Europium Ions in Eu-Doped Aluminate and Silicate Phosphors

Compounds of Sr3Al2O6 ： Eu, SrgAl14O25 ： Eu, and BaZnSiO4 ： Eu were synthesized by high-temperature solid state reactions. The doping Eu^3 ＋ ions were partially reduced to Eu^2＋ in Sr4Al14O25：Eu and BaZnSiOg：Eu prepared in an oxidizing atmosphere, N^2 ＋ O2. However, such an abnormal reduction process could not be performed in Sr3Al2O6：Eu, which was also prepared in an atmosphere of N^2 ＋ O2. Moreover, even though Sr3A1EO6：Eu was synthesized in a reducing condition CO, only part of the Eu^3 ＋ ions was reduced to Eu^2 ＋ . The existence of trivalent and divalent europium ions was confirmed by photoluminescent spectra. The different valence-change behaviors of europium ions in the hosts were attributed to the difference in host crystal structures. The higher the crystal structure stiffness, the easier the reduction process from Eu^3 ＋ to Eu^2 ＋ .

Preparation and luminescent properties of CaAl_2O_4:Eu^(3+),R^+(R=Li,Na,K) phosphors

CaAl2O4:Eu3+,R+(R=Li+,Na+,K+) red phosphors were synthesized by solid state reaction method.X-ray diffraction(XRD) and photoluminescence(PL) were employed to characterize their structural and luminescent properties.It was found that the optimal sintering temperature and sintering time were 1200 °C and 4 h,respectively.The optimal concentration of doped Eu3+ was 3 mol.%.Furthermore,under ultraviolet excitation with a wavelength of 254 nm,these samples showed red luminescence which were probably attributed to...

Luminescence properties of red-emitting Ca_2Al_2SiO_7:Eu^(3+) nanoparticles prepared by sol-gel method

A series of red-emitting Ca2_xA12SiOT：xEu^3＋ （x = 1 mol.%-10 tool.%） phosphors were synthesized by the sol-gel method. The effects of annealing temperature and doping concentration on the crystal structure and luminescence properties of Ca2A12SiO7：Eu^3＋ phosphors were investigated. X-ray diffraction （XRD） profiles showed that all peaks could be attributed to the tetragonal Ca2A12SiO7 phase when the sample was annealed at 1000℃. Scanning electron microscopy （SEM） micrographs indicate that the phosphors have an irregularly rounded mor- phology with particles of about 200 nm. Excitation spectra showed that the strong broad band at around 258 nm and weak sharp lines in 350-490 nm were attributed to the charge transfer band of Eu^3＋-O^2- and f-f transitions within the 4f^6 configuration of Eu^3＋ ions, respectively. Emission spectra implied that the red luminescence could be attributed to the transitions from the ^5D0 excited level to the 7Fj （J = 0, 1, 2, 3, 4） levels of Eu3＋ions with the main electric dipole transition ^5D0→^7F2 （618 and 620 nm）, and Eu^3＋ ions prefer to occupy a lower symmetry site in the crystal lattice. Moreover, the photoluminescence （PL） intensity was strongly dependent on both the sintering temperature and doping concentration, and the highest PL intensity was observed at an Eu^3＋ concentration x = 7 mol.% after annealing at ll00℃. The obtained Ca2A12SiO7：Eu^＋3＋ phosphor may have potential application for the red lamp phosphor.

Separation of Red (Y_2O_3: Eu^(3+)), Blue (Sr,Ca,Ba)_(10)(PO_4)_6Cl_2: Eu^(2+) and Green (LaPO_4:Tb^(3+),Ce^(3+)) Rare Earth Phosphors by Liquid/Liquid Extraction

A novel process for separation of red （Y2O3： Eu^3＋）, blue （Sr, Ca, Ba）10（PO4）6Cl2： Eu^2＋ and green （LaPO4： Tb^3＋, Ce^3＋） fine tricolor phosphor powders was established. First, the green phosphor was extracted and separated from three phosphor mixtures in heptane/DMF（N, N-Dimethylformamide） system using stearylamine or laurylamine （DDA） as the cationic surfactant. Then, after being treated with 99.5% ethanol, the blue and red phosphors could be separated in Heptane/DMF system in presence of 1-octanesulfonic acid sodium salt as the anionic surfactant. Satisfactory separation results have been achieved through two steps extractions with their artificial mixtures. The grades and recovery of separated products reached respectively as follows： red product was 95.3% and 90.9%, blue product was 90.0% and 95.2%, and green product was 92.2% and 91.8%.

Effect of Yb^(3+) concentration on the structures and upconversion luminescence properties of Y_2O_3:Er^(3+) ultrafine phosphors

Y2O3：Er^3＋ ultrafine phosphors with a varying Yb^3＋ ion concentration were prepared by a urea homogeneous precipitation method. The results of XRD show that all the samples are of a pure cubic structure and the average crystallite sizes can be calculated as 45, 34, and 28 nm for Y2O3：Er^3＋ ultrafine phosphors with Yb^3＋ ion concentrations of 0, 10%, and 20%, respectively. The lattice constant and cell volume of the ultrafine phosphors decrease with enhancing Yb^3＋ ion concentration. The upconversion luminescence spectra of all the samples were studied under 980 nm laser excitation. The strong green and red upconversion emission were observed, and attributed to the ^2H11/2→^4I15/2, ^4S3/2 → ^4I15/2 and ^4F9/2 →^4I15/2 transitions of Er^3＋, respectively. The intensity of red emission increases with increasing Yb^3＋ ion concentration. The effect of Yb^3＋ ion concentration on the structures and upconversion luminescence mechanism were discussed.

Synthesis and Characterization of Cerium-Doped Lutetium Aluminum Garnet Phosphors by Nitrate-citrate Sol-Gel Combustion Process

Nanosized cerium-doped lutetium aluminum garnet （LuAG：Ce） phosphors were prepared by nitrate-citrate solgel combustion process using 1：1 ratio of the citrate：nitrate. The prepared LuAG：Ce phosphors were characterized by XRD, TEM, photoluminescence and radioluminescence spectra excited by UV and X-ray, respectively. The purified crystalline phase of LuAG：Ce was obtained at 900 ℃ by directly crystallizing from amorphous materials. The resultant Lu- AG：Ce phosphors were uniform and had good dispersivity with an average particle size of about 30 urn. Both photoluminescence and radioluminescence were well-known Ce^3＋ emissions located in the range of 470 -600 nm consisting of two emission bands because of the transition from the lowest 5d excited state （2D） to the 4f ground state of Ce^3＋, which matched well with the sensitivity curve of the Si-photodiode. There was a little red shift for the emission components from the UV-excited emission spectrum to the X-ray-excited emission spectrum. The fast scintillation decay component of 26 ns satisfies the requirements of fast scintillators.

Effect of fluxes on structure and luminescence properties of Y_3Al_5O_(12):Ce^(3+) phosphors

Ce3＋-activated yttrium aluminum garnet （YAG） was prepared by the solid-state reaction, in which H3BO3, LiF, NaF, KF and BaF2 were used as the fluxes. The effect of fluxes on optical properties of phosphors was studied in detail, especially the fluxes of alkali fluorides, which could enhance the emission intensity and change the wavelength of emission peaks. Among these YAG：Ce phosphors, the phosphor sintered with H3BO3 and NaF exhibited the strongest emission. The emission peaks of phosphors prepared with fluxes from LiF to KF were shifted to long wavelength. The effect of NaF concentration on the emission intensity of YAG：Ce was also investigated. The value of emission intensity reached the maximum when the concentration of NaF was 0.5%.