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.

Preparation and characterization of Eu^(3+)-doped CaCO_3 phosphor by microwave synthesis

A Eu^3＋-doped CaCO3 phosphor with red emission was prepared by microwave synthesis. The scanning electron microscopy （SEM） image and laser particle size analysis show that the CaCO3：Eu^3＋ particles are needle-like in the length range of 5.0-10.0 μm. The results of X-ray diffraction （XRD） analysis, Fourier transform infrared spectroscopy （FT-IR）, and Raman spectroscopy indicate that pure aragonite CaCO3：Eu^3＋ is prepared using microwave irradiation and the Eu^3＋ ion as a luminescence center inhabits the site of Ca^2＋. The photoluminescence excitation （PLE） spectrum shows that the strong broad band at around 270 nm and weak sharp lines in 300-550 nm are assigned to the charge transfer band of Eu^3＋-O^2- and intra-configurational 4f-4f transitions of Eu^3＋, respectively. The photoluminescence （PL） spectrum implies that the red luminescence can be attributed to the transitions from the ^5D0 excited level to the ^7FJ （J = 0, 1, 2, 3, 4） levels of Eu^3＋ ions with the mainly electric dipole transition ^5D0 → ^7F2 （614 and 620 nm）, and the Eu^3＋ ions prefer to occupy the low symmetric site in the crystal lattice.

Interpretation of the 4f-5d Excitation Spectra of Eu^(3+) and Tb^(3+) Doped in Crystals

The structure of the low-temperature 4f^N→4f^N-15d excitation spectra of Eu^3＋ and Tb^3＋ doped in crystals LiYF4, YPO4 and CaF2 measured by van Pieterson et al. in 2002 was analyzed and assigned based on the simple model proposed by Duan and co-workers in the last few years. Some complemental discussion on effects of J-mixing on the f-d transition intensities for Eu^3＋ due to the f-electron crystal-field interaction Hcf（f）, which was ignored in the simple mod- el, was presented. Some previously unexplained peaks for Tb^3 ＋ were interpreted to be spin-forbidden transitions to higher 5d crystal-field levels, or assigned to be f→d excitations with the core 4f7 excited from ^8S to ^6P, ^6I and ^6D, respectively. It is shown that the main structure of 4f-Sd excitation spectra of Eu^3＋ and Tb^3＋ can be well interpreted with the simple model.

Structure and Luminescence Properties of Eu^(3+) Doped SiO_2 Glass Synthesized by Sol-Gel Process

Under different annealing temperatures, Eu 3+ doped SiO 2 gel and glass were prepared by sol gel method, and the structure and luminescent properties were studied with excitation spectra, emission spectra, IR and DTA TG. The results show that the fluorescent intensity tends to get stable when concentration of Eu 3+ doped is above 1 86 % (mass fraction) most water absorbed by the gel was removed at 300 ℃, and that the emission spectrum of Eu 3+ , with peaks at 614, 588, 577 nm, is due to 5D 0→ 7F 2, 5D 0→ 7F 1, 5D 0→ 7F 0 transitions, and the excitation peaks at 318, 362, 380, 393, 412 and 462 nm were observed. These results illustrate that the temperature range of 300～500 ℃ is critical for the structure conversion from gel to glass, and the fluorescence is strongly quenched by water.

Effects of Heat-treatment Temperature on Eu^(3+) and Li^+ Co-doped ZnO Photoluminescence by Sol-gel Process

The photoluminescence （PL） characteristics of Eu^3＋ and Li^＋ co-doped ZnO PL materials against heat-treatment temperature were discussed. The PL xerogel and powder samples were prepared by solgel process. The emission spectra of all samples showed two broad bands peaking at 590 nm and 620 nm under UV-Vis excitation. But the relative intensity of red PL （620 nm） was much greater than that of green PL （590 nm） of the same sample, that s to say, the red color was the main luminescence. With heat-treatment temperature increase, the two kinds of colors PL intensity decreased, and both the red and green PL intensity of the xerogel samples was much greater than those of powder samples respectively. The XRD patterns revealed that Eu^3＋ ions were successfully incorporated in ZnO crystals in xerogel samples. When heat-treatment temperature reached 350 ℃, the Eu^3＋ began to separate out of the ZnO crystals and Eu2O3 crystals came into being. When the powder sample was subjected to UV-Vis excitation, the energy transfered from the host ZnO emission to Eu^3＋ became weaker than the xerogel sample.

Luminescence properties of YAl_3(BO_3)_4 phosphors doped with Eu^(3+) ions

YAl3 （BO3）4： Eu^3＋ phosphors were prepared by the conventional solid state reaction. The phase structure and morphology were investigated by X-ray diffraction （XRD） and scanning electron microscope （SEM）. Doping YAl3（BO3）4： Eu^3＋ phosphors with concentration of Eu^3＋ ions of 0, 2, 5, 8 and 10 mol% were studied and their luminescent properties at room temperature were discussed. The excitation spectrum of Y0.95Eu0.05Al3（BO3）4 was composed of a broad band centered at about 252 nm and a group of lines in the longer wavelength region. In the emission spectra, the peak wavelength was about 614 nm under a 252 nm UV excitation. The optimal doping concentration of Eu^3＋ ions in YAl3（BO3）4： Eu^3＋ phosphors was 8 mol%.

Photoluminescence of BaGdB_9O_(16):Eu^(3+) co-doped Al^(3+) or Sc^(3+) under UV-VUV excitation

Single phase of BaGd0.9-xMxEu0.1B9O16（M=Al or Sc, 0≤x≤0.3） powder was prepared by the solid-state reaction and its photoluminescence（PL） properties were investigated under ultraviolet（UV） and vacuum ultraviolet（VUV） excitation.Monitored with 613 nm emission, the excitation spectra of BaGd0.9-xMxEu0.1B9O16 consisted of three broad bands peaking at about 242, 208, and 142 nm, respectively.The one at about 242 nm originated from the charge transfer band（CTB） of O2-→Eu^3＋.The other two were assigned to the absorption of the host, which was overlapped with absorptions among borate groups, f→d transition of RE3＋（RE=Gd, Eu）, and the charge transfer transition of O2-→Gd^3＋.The maximum emission peak was observed at about 613 nm in the emission spectra of BaGd0.9-xMxEu0.1B9O16 under both 254 and 147 nm excitation, which originated from the electric dipole 5D0→7F2 transition of Eu^3＋.When excited with 254 nm, the integral emission intensity of Eu^3＋ increased after Al^3＋ or Sc^3＋ substituting Gd^3＋ partly in BaGd0.9Eu0.1B9O16.Under 147 nm excitation, the integral emission intensity of Eu^3＋ decreased after some Gd^3＋ was replaced by Sc^3＋, but increased after adding appropriate Al^3＋ into BaGd0.9Eu0.1B9O16.

Enhanced Emission of Eu^(3+) in Boron Ions-Doped Sol-Gel SiO_2 Phosphors

Al-doped and B, Al-codoped silica xerogel was fabricated by sol-gel process. The influence of B ions and annealing temperature on luminescent properties of phosphors were studied by using fluorescence spectrum, X-ray diffraction, DSC, TG/DTG analysis and IR spectrum. The heat treatment has a large effect on the luminescent properties. Under 248 nm excitation, the emission spectrum of samples heated shows characteristic emission peaks of Eu^3＋ ions are, which are due to the transitions of ^5D0→^7FJ（J = 0, 1, 2, 3, 4） of Eu^3＋ , respectively. The transition of ^5D0→^7F1 is split into two peaks.

Improving luminescent property of SrIn_2 O_4 :Eu^(3+) by co-doped A^+ (A = Li, Na, K) or Sm^(3+)

A series of SrIn2 O4 ：Eu^3＋ phosphors are synthesized by a high temperature solid-state method, and their luminescent properties are investigated. They can be excited by 395-nm radiation, and produce red emission （619 nm）; however, they have a low absorption of near-ultraviolet light with the wavelength of 400nm–405 nm. When co-doped with A^＋ （A=Li, Na, K）, the emission intensity of SrIn2O4 ：Eu^3＋ is significantly enhanced, but its emission and excitation spectral profile is unchanged. With co-doping Sm^3＋ , not only is the emission intensity of SrIn2 O4 ：Eu^3＋ enhanced, but also the absorption is broadened and strengthened in the range of 400 nm–405nm. The effect of Sm^3＋ -doped content on the emission intensity of SrIn2O4 ：Eu^3＋ , Sm^3＋ is investigated, and the optimal Sm^3＋ content is 0.02 mol.

Spectral Properties and Sensitization of Ce^(3+) and Eu^(2+) Codoped Calcium Zinc Chlorosilicate

The Ce^3+ and Eu^2+ ions codoped calcium zinc chlorosilicate Ca_8Zn(SiO_4)_4Cl_2 phosphors have been synthesized for the first time. The diffuse reflection, excitation and emission spectra of Ca_8Zn(SiO_4)_4Cl_2∶Ce^3+, Eu^2+ have been measured at room temperature. The luminescence sensitizaiton of Eu^2+ by Ce^3+ inCa_8Zn(SiO_4)_4Cl_2∶Ce^3+, Eu^2+ has been expounded under the excitation of ultraviolet light and the efficient nonradiative energy transfer from Ce^3+ to Eu^2+ in this system is confirmed.

Site Selective Spectra of Eu^(3+)-Doped Y_2SiO_5 Crystal

By using a whitelight lamp, an Ar+ ion laser whosewavelength was tuned to 457. 9 nmand a tunable Rh 6G dye laser(linewidth: 0. 5 cm-1) pumped bythe second harmonic of a Nd: YAGlaser as light sources and using amonochromator, a phase-lockingamplifier and a computer as the data detecting system, the transmission spectrum, fluorescence spectra, excitation spectrum and siteselective fluorescence spectra ofthe Eu3+: Y2SiO5 crystal were observed. More than thirty out of thetotal fifty spectral lines were observed for 5D0→7F0,1,2,3,4 transitions. The Eu3+ ions occupy twokinds of the Y3+ sites with the lowsymmetry in this crystal. The difference of the wavelengths of thetwo Eu3+ sites for 7F0→5D0 transition is about 0. 2 nm. It was foundthat the two sites were nonequivalent optical ones at room temperature. Crystal lattice constants a,b, c, and β of Eu3+: Y2SiO5 werealso measured by the X-ray diffraction method. The results show thatthe lattice constants a, b, and cof the crystal doped Eu3+ ions isvery close to those of the Y2SiO5crystal undoped Eu3+ ions.

Persistent Spectral Hole Burning of Eu^3＋ Doped Y2SiO5 Crystal at 579.62 nm

By using an Ar^＋ ion laser, a tunable Rh6G dye laser（linewidth： 0.5 cm^-1） pumped by the second harmonic of a YAG：Nd laser and an 899-21 dye laser as light sources and using a monochromator, a phase-locking amplifier and a computer as the data detecting system, the spectra and spectral hole burning of Eu^3＋：Y2SiO5 crystal were researched in this paper.Photoluminescence excitation spectrum and site selective fluorescence spectrum were detected at room temperature and 77 K. Hole burning experiments were reached at 16 K. A spectral hole with hole width of about 80 MHz were detected and it could be kept for 10 h.

Quenching Study on Iron Impurity in Eu^(2+), Dy^(3+) Doped Strontium Aluminate Phosphor Prepared by Nano-Coating Process

A series of long afterglow phosphors, Eu2+, Dy3+, with different iron content were prepared by nano-coating process. The resulted precursors were characterized by Transmission Electron Microscope (TEM), which suggested that the precursor particles had nanometer size distribution. The optical quenching of iron impurity on the phosphor powders were investigated by X-Ray powder Diffraction (XRD) and photoluminescence methods. The XRD indicates that a pure monoclinic SrAl2O4∶Eu2+, Dy3+ was formed at 1200 ℃ and iron impurity up to 296.36×10-4% had no effect on the SrAl2O4∶Eu2+, Dy3+ phase structure. However, the luminescence intensity were strongly dependent on the trace iron impurity, which might be explained that iron displace the aluminium and form Fe-O bond, which competed energy with Eu2+ and transfer red them to infrared sites.

Luminescent characteristics of Tm^(3+)/Tb^(3+)/Eu^(3+) tri-doped Na_(5)Y_(9)F_(32) single crystals for white emission with high thermal stability

By using an improved Bridgman method,0.3 mol%Tm^(3+)/0.6 mol%Tb^(3+)/y mol%Eu^(3+)(y=0,0.4,0.6,0.8)doped Na_(5)Y_(9)F_(32)single crystals were prepared.The x-ray diffraction,excitation spectra,emission spectra and fluorescence decay curves were used to explore the crystal structure and optical performance of the obtained samples.When excited by 362 nm light,the cool white emission was realized by Na_(5)Y_(9)F_(32)single crystal triply-doped with 0.3 mol%Tm^(3+)/0.6 mol%Tb^(3+)/0.8 mol%Eu^(3+),in which the Commission Internationale de l’Eclairage(CIE)chromaticity coordinate was(0.2995,0.3298)and the correlated color temperature(CCT)was 6586 K.The integrated normalized emission intensity of the tridoped single crystal at 448 K could keep 62%of that at 298 K.The internal quantum yield(QY)was calculated to be~15.16%by integrating spheres.These results suggested that the single crystals tri-doped with Tm^(3+),Tb^(3+)and Eu^(3+)ions have a promising potential application for white light-emitting diodes(w-LEDs).

高压水蒸气对β-Li_(2)TiO_(3:)Eu^(3+)荧光粉的全谱发光性能影响

采用水热法制备荧光粉前驱体后通过高温煅烧的方法,合成了由电偶极跃迁主导的高色纯度的β-Li_(2)TiO_(3):Eu^(3+)红色荧光粉.设计了适用于DHT11的拓扑电路,对荧光粉体湿度和温度进行测试.研究发现,高压腔体中加水量为5 mL,β-Li_(2)TiO_(3):0.5 mol%Eu^(3+)的相对湿度可达81%RH.在波长为396 nm的近紫外光激发下,β-Li_(2)TiO_(3):0.5 mol%Eu^(3+)发射由电偶极跃迁主导的613 nm的红光,荧光寿命为773.36μs,高压水蒸气处理对β-Li_(2)TiO_(3):0.5 mol%Eu^(3+)的电偶极跃迁发射峰和磁偶极跃迁发射峰位置没有变化,但发射峰强度增强并且荧光寿命降至386.81μs.高压水蒸气高压处理后的荧光粉色坐标x=0.47,y=0.51,色温为3300 K,红光色纯度为96.6%,比高压处理前显示出更优异的显色性能.高压水蒸气处理后的β-Li_(2)TiO_(3):0.5 mol%Eu^(3+)电偶极跃迁谱线强度参数Ω_(2)增加至4.21×10^(-19)cm^(2),^(5)D_(0)→^(7)F_(2)跃迁的荧光分支比β2也增加至96.9%,而量子效率η减小至57%,证实了湿度对荧光粉的发光效率具有极大的影响.

Bi^(3+)、Eu^(3+)共掺杂La_(4)GeO_(8)荧光粉的制备及可调发光

为了开发出高效稳定的单一基质白光发射荧光材料,本工作通过高温固相法成功合成了一系列La_(4)GeO_(8)∶Bi^(3+),Eu^(3+)荧光粉样品,并通过X射线衍射、室温光谱、变温光谱等手段研究了实验样品的结构与发光性能。研究发现,Bi^(3+)离子在该结构中占据两种不同的格位(Bi^(3+)(Ⅰ)和Bi^(3+)(Ⅱ)),且在紫外光激发下呈现两个峰值分别在475 nm和620 nm的宽带发射。对于Bi^(3+)、Eu^(3+)共掺样品,由于Bi^(3+)(Ⅰ)与Eu^(3+)之间的竞争吸收、Bi^(3+)(Ⅰ)至Bi^(3+)(Ⅱ)以及Bi^(3+)(Ⅱ)至Eu^(3+)的能量传递作用,可实现蓝色至红色、橙红色至红色的可调发光。特别地,样品La_(4)GeO_(8)∶0.07Bi^(3+),0.06Eu^(3+)在313 nm光激发下可获得CIE值为(0.335,0.319)的优异白色发光。此外,该白光发射材料具有较佳的发光热稳定性,当温度升高至380 K时,发光积分强度仍然为室温的59%,表明其在白光二极管上具有潜在的应用价值。

基于Eu^(3+)-生物质碳量子点探针的比率型荧光传感体系检测盐酸四环素

该文以橙皮为原料制备的碳量子点(CDs)与铕离子(Eu^(3+))构建双发射比率型荧光探针(Eu^(3+)-CDs)并用于抗生素盐酸四环素的检测。在370 nm激发波长下,Eu^(3+)-CDs荧光探针在425 nm处出现较强的蓝色荧光峰,在617 nm处出现较弱的红色荧光峰。随着盐酸四环素浓度的逐渐增大,Eu3+与盐酸四环素螯合形成的配合物增多,在425 nm处的CDs荧光(I_(F425))逐渐减弱,而617 nm处铕配合物的荧光(I_(F617))逐渐增强,可基于荧光强度比I_(F617)/I_(F425)的变化对盐酸四环素进行测定。考察了Eu^(3+)的浓度、pH值和反应时间对探针荧光强度的影响。在最佳条件下,该双发射比率型荧光探针对盐酸四环素具有特异性识别能力,荧光强度比(I_(F617)/I_(F425))与盐酸四环素浓度在10~100µmol/L范围内存在良好的线性关系,相关系数r^(2)=0.9926,检出限为5.09µmol/L。该方法成功用于猪肉中盐酸四环素含量的检测,加标回收率为102%~110%,相对标准偏差为0.20%~2.4%,具有较好的实用性。

Effect of Er substituting sites on upconversion luminescence of Er^(3+)-doped BaTiO_3 films

Erbium-doped BaTiO3 films on LaNiO3/Si substrates were fabricated by sol-gel method. The crystalline structure, morphologies and upconversion （UC） luminescence properties of films were respectively investigated by X-ray diffraction （XRD）, atomic force microcopy （AFM） and photoluminescence （PL）. The results indicate that both of the microstructure and luminescence are found to be dependent on Er^3＋ substituting sites. The samples with A-site substitution have smaller lattice constants, larger grains and smoother surface than those with B-site substitution. The photoluminescence spectra show that both of the samples have two stronger green emission bands centered at 528 and 548 nm and a weak red emission band centered at 673 nm, which correspond to the relaxation of Er^3＋ from ^2H11/2, ^4S3/2, and ^4F9/2 levels to the ground level ^4I15/2, respectively. Compared with B-site doped films, A-site doped films have a stronger integrated intensity of green emissions and a weaker relative intensity of red emissions. The differences could be explained by the crystalline quality and cross relaxation （CR） process.

用于痕量监测Zr^(4+)、Cr_(2)O_(7)^(2-)、Fe^(3+)、HPO_(4)^(2-)和指纹识别的功能化Eu^(3+)/Tb^(3+)配位聚合物荧光探针的构筑

采用芳香族π共轭及含氮原子有机连接剂,合成同构铽、铕发光配位聚合物(CPs){[Eu(PLIA)_(1.5)(H_(2)O)_(2)]·H_(2)O}_(n)(1)和{[Tb(PLIA)_(1.5)(H_(2)O)_(2)]·H_(2)O}_(n)(2),其中H_(2)PLIA=5-((吡啶-4-基甲基)氧基)苯-1,3-二甲酸。对合成的配合物进行了结构测定、表征和荧光痕量识别实验研究。2个同构配合物具有理想的三维框架结构,π…π堆积及氢键等弱相互作用增强了其化学稳定性;表征显示配位聚合物1和2具有良好的荧光性质、结晶性、热力学稳定性及结构完整性,可作为荧光传感的材料。1和2对水溶液中的Zr^(4+)、Cr_(2)O_(7)^(2-)和Fe^(3+)、HPO_(4)^(2-)具有选择性好、灵敏度高的荧光识别能力,其检出限分别为0.139μmol·L^(-1)(1,Zr^(4+))、0.626μmol·L^(-1)(1,Cr_(2)O_(7)^(2-))、0.430μmol·L^(-1)(2,Fe^(3+))、1.36μmol·L^(-1)(2,HPO_(4)^(2-))。探究了1和2作为探针的荧光猝灭机理。更有趣的是,1和2具有指纹识别性能,其荧光指纹纹路清晰连贯,细节明显,可被清晰观察。

Preparation of Zr-doped CaTiO_3 with enhanced charge separation efficiency and photocatalytic activity

A series of Zr-doped CaTiO3 powders were prepared with the mild co-precipitation method and calcined at 850℃ for 3 h. The as-prepared Zr-doped CaTiO3 samples were characterized by scanning electron microscopy （SEM）, X-ray diffraction （XRD）, UV-Vis diffuse reflectance spectra （DRS） and X-ray photoelectron spectra （XPS）. XRD result revealed the presence of single perovskite phase of CaTiO3. UV-Vis diffusive reflection spectra of Zr-doped CaTiO3 indicated that the absorbance obviously increased in the visible light irradiation. XPS analysis showed that two types of oxygen existed on the photocatalyst surface, including lattice oxygen and absorbed oxygen. Their photocatalytic activity in the case of the degradation of methyl orange in water and photoelectrochemical activity were also tested. The 5%Zr-doped （mole fraction） CaTiO3 sample showed the highest photocatalytic activity. The enhanced photocatalytic activity was ascribed to the change of the lattice structure, existence of oxygen vacancies and increase of the photogenerated charge separation efficiency.