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1.
《化学:亚洲杂志》2017,12(12):1353-1363
Rare‐earth borates are good candidates for optical applications. To date, however, the high‐pressure/high‐temperature technique has produced a large number of novel borates with optical properties that have rarely been investigated due to the severe problem of substantial defects. We targeted the high‐pressure polymorph of β‐GdB3O6 and synthesized three solid solutions of β‐Gd0.75−x Bi0.25Tbx B3O6 (0≤x ≤0.75), β‐Gd0.75−y Bi0.25Euy B3O6 (0≤y ≤0.75), and β‐Gd0.50−z Bi0.25Tb0.25Euz B3O6 (0≤z ≤0.05) by using typical solid‐state reactions at 820 °C. Here, the function of Bi3+ is to stabilize the high‐pressure phase by lowering the synthetic temperature and being the sensitizer to promote the green and red emissions of Tb3+ and Eu3+. The multiple energy transfer paths were investigated by using lifetime decay experiments and photoluminescent spectra, and both efficiency and mechanism were determined. Eventually, color‐tunable and white emissions were achieved by rational doping of Bi3+, Tb3+, and Eu3+ into β‐GdB3O6, that is, the CIE chromaticity coordinate for β‐Gd0.44Bi0.25Tb0.30Eu0.01B3O6 is (0.318, 0.365) with a correlated color temperature of 6101 K.  相似文献   

2.
A series of Eu3+ ions co-doped (Gd0.9Y0.1)3Al5O12:Bi3+, Tb3+ (GYAG) phosphors have been synthesized by means of solvothermal reaction method. The XRD pattern of GYAG phosphor sintered at 1500 °C confirms their garnet phase. The luminescence properties of these phosphors have been explored by analyzing their excitation and emission spectra along with their decay curves. The excitation spectra of the GYAG:Bi3+, Tb3+, Eu3+ phosphors consists of broad bands in the shorter wavelength region due to 4f8 → 4f75d1 transition of Tb3+ ions overlapped with 6s2 → 6s16p1 (1S0 → 3P1) transition of Bi3+ ions and the charge transfer band of Eu3+–O2?. The present phosphors exhibit green and red colors due to 5D4 → 7F5 transition of Tb3+ ions and 5D0 → 7F1 transition of Eu3+ ions, respectively. The emission was shifted from green to red color by co-doping with Eu3+ ions, which indicate that the energy transfer probability from Tb3+ to Eu3+ ions are dependent strongly on the concentration of Eu3+ ions.  相似文献   

3.
In this work, a latent energy-transfer process in traditional Eu3+,Tb3+-doped phosphors is proposed and a new class of Eu3+,Tb3+-doped Na4CaSi3O9 (NCSO) phosphors is presented which is enabled by luminescence decay dynamics that optimize the electron-transfer energy process. Relative to other Eu3+,Tb3+-doped phosphors, the as-synthesized Eu3+,Tb3+-doped NCSO phosphors show improved large-scale tunable emission color from green to red upon UV excitation, controlled by the Tb3+/Eu3+ doping ratio. Detailed spectroscopic measurements in the vacuum ultraviolet (VUV)/UV/Vis region were used to determine the Eu3+–O2− charge-transfer energy, 4f–5d transition energies, and the energies of 4f excited multiplets of Eu3+ and Tb3+ with different 4fN electronic configurations. The Tb3+→Eu3+ energy-transfer pathway in the co-doped sample was systematically investigated, by employing luminescence decay dynamics analysis to elucidate the relevant energy-transfer mechanism in combination with the appropriate model simulation. To demonstrate their application potential, a prototype white-light-emitting diode (WLED) device was successfully fabricated by using the yellow luminescence NCSO:0.03Tb3+, 0.05Eu3+ phosphor with high thermal stability and a BaMgAl10O17:Eu2+ phosphor in combination with a near-UV chip. These findings open up a new avenue to realize and develop multifunctional high-performance phosphors by manipulating the energy-transfer process for practical applications.  相似文献   

4.
The multicolor Gd2O2S:xTb3+, yEu3+ hollow spheres were successfully synthesized via a template-free solvothermal route without the use of surfactant from commercially available Ln (NO3)3·6H2O (Ln = Gd, Tb and Eu), absolute ethanol, ethanediamine and sublimed sulfur as the starting materials. The phase, structure, particle morphology and photoluminescence (PL) properties of the as-obtained products were investigated by X-ray diffraction (XRD), fourier transform infrared spectroscopy (FT-IR), field emission scanning electron microscopy (FE-SEM) and photoluminescence spectra. The influence of synthetic time on phase, structure and morphology was systematically investigated and discussed. The possible formation mechanism depending on synthetic time t for the Gd2O2S phase has been presented. These results demonstrate that the Gd2O2S hollow spheres could be obtained under optimal condition, namely solvothermal temperature T = 220 °C and synthetic time t = 16 h. The as-obtained Gd2O2S sample possesses hollow sphere structure, which has a typical size of about 2.5 μm in diameter and about 0.5 μm in shell thickness. PL spectroscopy reveals that the strongest emission peak for the Gd2O2S:xTb3+ and the Gd2O2S:yEu3+ samples is located at 545 nm and 628 nm, corresponding to 5D47F5 transitions of Tb3+ ions and 5D07F2 transitions of Eu3+ ions, respectively. The quenching concentration of Tb3+ ions and Eu3+ ions is 7%. In the case of Tb3+ and Eu3+ co-doped samples, when the concentration of Tb3+ or Eu3+ ions is 7%, the optimum concentration of Eu3+ or Tb3+ ions is determined to be 1%. Under 254 nm ultraviolet (UV) light excitation, the Gd2O2S:7%Tb3+, the Gd2O2S:7%Tb3+,1%Eu3+ and the Gd2O2S:7%Eu3+ samples give green, yellow and red light emissions, respectively. And the corresponding CIE coordinates vary from (0.3513, 0.5615), (0.4120, 0.4588) to (0.5868, 0.3023), which is also well consistent with their luminous photographs.  相似文献   

5.
Excitation of Tb3+ and Eu3+ in DMSO with 487 mμ, which corresponds to the 7F65D4 transition of Tb3+, is accompanied by a reduction in the fluorescence efficiency of Tb3+ as [Eu3+] increases and by the appearance of a weak emission from Eu3+. An average rate constant for both the fluorescence quenching of Tb3+ and the energy transfer from Tb3+ to Eu3+ with subsequent emission from the latter, was found to be (2.2 ± 0.4) × 103 M?1 sec?1.  相似文献   

6.
采用优化的高温固相方法制备了稀土离子Eu3+和Tb3+掺杂的La7O6(BO3)(PO42系荧光材料,并对其物相行为、晶体结构、光致发光性能和热稳定性进行了详细研究。结果表明,La7O6(BO3)(PO42:Eu3+材料在紫外光激发下能够发射出红光,发射光谱中最强发射峰位于616 nm处,为5D07F2特征能级跃迁,Eu3+的最优掺杂浓度为0.08,对应的CIE坐标为(0.610 2,0.382 3);La7O6(BO3)(PO42:Tb3+材料在紫外光激发下能够发射出绿光,发射光谱中最强发射峰位于544 nm处,对应Tb3+5D47F5能级跃迁,Tb3+离子的最优掺杂浓度为0.15,对应的CIE坐标为(0.317 7,0.535 2)。此外,对2种材料的变温光谱分析发现Eu3+和Tb3+掺杂的La7O6(BO3)(PO42荧光材料均具有良好的热稳定性。  相似文献   

7.
A series of novel KBaSc2(PO4)3:Ce3+/Eu2+/Tb3+phosphors are prepared using a solid‐state reaction. X‐ray diffraction analysis and Rietveld structure refinement are used to check the phase purity and crystal structure of the prepared samples. Ce3+‐ and Eu2+‐doped phosphors both have broad excitation and emission bands, owing to the spin‐ and orbital‐allowed electron transition between the 4f and 5d energy levels. By co‐doping the KBaSc2(PO4)3:Eu2+ and KBaSc2(PO4)3:Ce3+ phosphors with Tb3+ ions, tunable colors from blue to green can be obtained. The critical distance between the Eu2+ and Tb3+ ions is calculated by a concentration quenching method and the energy‐transfer mechanism for Eu2+→Tb3+ is studied by utilizing the Inokuti–Hirayama model. In addition, the quantum efficiencies of the prepared samples are measured. The results indicate that KBaSc2(PO4)3:Eu2+,Tb3+ and KBaSc2(PO4)3:Ce3+,Tb3+ phosphors might have potential applications in UV‐excited white‐light‐emitting diodes.  相似文献   

8.
Lanthanide sensitized luminescence and chemiluminescence (CL) are of great importance because of the unique spectral properties, such as long lifetime, large Stokes shifts, and narrow emission bands characteristic to lanthanide ions (Ln3+). With the fluoroquinolone (FQ) compounds including enoxacin (ENX), norfloxacin (NFLX), lomefloxacin (LMFX), fleroxacin (FLRX), ofloxacin (OFLX), rufloxacin (RFX), gatifloxacin (GFLX) and sparfloxacin (SPFX), the luminescence and CL properties of Tb3+–FQ and Eu3+–FQ complexes have been investigated in this contribution. Ce4+–SO32− in acidic conditions was taken as the CL system and sensitized CL intensities of Tb3+–FQ and Eu3+–FQ complexes were determined by flow-injection analysis. The luminescence and CL spectra of Tb3+–FQ complexes show characteristic peaks of Tb3+ at 490 nm, 545 nm, 585 nm and 620 nm. Complexes of Tb3+–ENX, Tb3+–NFLX, Tb3+–LMFX and Tb3+–FLRX display relatively strong emission intensity compared with Tb3+–OFLX, Tb3+–RFX, Tb3+–GFLX and Tb3+–SPFX. Quite weak peaks with unique characters of Eu3+ at 590 nm and 617 nm appear in the luminescence and CL spectra of Eu3+–ENX, but no notable sensitized luminescence and CL of Eu3+ could be observed when Eu3+ is added into other FQ. The distinct differences on emission intensity of Tb3+–FQ and Eu3+–FQ might originate from the different energy gap between the triplet levels of FQ and the excited levels of the Ln3+. The different sensitized luminescence and CL signals among Tb3+–FQ complexes could be attributed to different optical properties and substituents of these FQ compounds. The detailed mechanism involved in the luminescence and CL properties of Tb3+–FQ and Eu3+–FQ complexes has been investigated by analyzing the luminescence and CL spectra, quantum yields, and theoretical calculation results.  相似文献   

9.
A series of phosphors SrBPO5:R,Na+ (R = Eu3+, Tb3+) were prepared by high-temperature solid-state synthesis, and their phase purity, morphology, IR spectra, and UV-Vis photoluminescence properties were investigated. The f-f transitions of Eu3+ and Tb3+ ions in the host lattice were assigned and discussed. The excitation and emission spectra indicate that SrBPO5:Eu3+,Na+ and SrBPO5:Tb3+,Na+ can be effectively excited by ultraviolet (394 and 370 nm), and exhibit reddish orange emission and yellowish green emission, respectively. The influence of the doping concentration on the relative emission intensity of Eu3+/Tb3+ was investigated, and the critical distance Rc was estimated in term of the concentration quenching data. The present study suggests SrBPO5:R,Na+ (R = Eu3+, Tb3+) phosphor can be a potential candidate as an UV-convertible phosphor for white light-emitting diodes (LEDs).  相似文献   

10.
The polychromatic emission and wide-range color tuning in the luminescent nanoparticles are currently of crucial importance, due to the development of color and white light-emitting diode (LED) devices, based on such lanthanide-doped nanostructured materials. By utilization of precipitation method, Tb3+-doped and Tb3+/Eu3+-codoped NaYbF4 nanoparticles (i.e. NPs) are synthesized. For Tb3+-doped NaYbF4 NPs excited by 377 nm, green emission originating from Tb3+ is observed, where its optimum state is obtained when Tb3+ content is 25 mol% and the concentration quenching mechanism is found by electric dipole-dipole interaction. Moreover, due to the existence of energy transfer between Tb3+ and Eu3+, polychromatic emissions are realized in Tb3+/Eu3+-codoped NaYbF4 NPs as Eu3+ content increases. Through analyzing emission decay times and emission spectra, it was confirmed that the energy transfer mechanism in the synthesized NPs is governed mainly by electric dipole-dipole interaction. Furthermore, the resultant NPs also own strong resistance to temperature, which is verified by temperature-dependent emission spectra, and the activation energies of Tb3+ and Eu3+ are 0.206 and 0.207 eV, respectively. In addition, by employing designed NPs as yellow-emitting components, the fabricated white-LED emits brightness warm white light with color coordinate of (0.385, 0.380), high color rendering index of 84.3 and low correlated color temperature of 3903 K. This work does not only offer an available route to develop NPs with polychromatic emissions but also devise promising luminescent materials for improving the performance of the phosphor-converted white-LED.  相似文献   

11.
In recent years, luminescent materials doped with Ln3+ ions have attracted much attention for their application as optical thermometers based on both downshifting and upconversion processes. This study presents research done on the development of highly sensitive optical thermometers in the physiological temperature range based on poly(methyl methacrylate) (PMMA) films doped with two series of visible Ln3+ complexes (Ln3+=Tb3+, Eu3+, and Sm3+) and SiO2 nanoparticles (NPs) coated with these PMMA films. The best performing PMMA film doped with Tb3+ and Eu3+ complexes was the PMMA[TbEuL1tppo]1 film (L1=4,4,4-trifluoro-1-phenyl-1,3-butadionate; tppo=triphenylphosphine oxide), which showed good temperature sensing of Sr=4.21 % K−1 at 313 K, whereas for the PMMA films doped with Tb3+ and Sm3+ complexes the best performing was the PMMA[TbSmL2tppo]3 film (L2=4,4,4-trifluoro-1-(4-chlorophenyl)-1,3-butadionate), with Sr=3.64 % K−1 at 313 K. Additionally, SiO2 NPs coated with the best performing films from each of the series of PMMA films (Tb–Eu and Tb–Sm) and their temperature-sensing properties were studied in water, showing excellent performance in the physiological temperature range (PMMA[TbEuL1tppo]1@SiO2: Sr=3.84 % °C at 20 °C; PMMA[TbSmL2tppo]3@SiO2: Sr=3.27 % °C at 20 °C) and the toxicity of these nanoparticles on human cells was studied, showing that they were nontoxic.  相似文献   

12.
Cooperative performance of mixed‐valent Eu2+/Eu3+ in single‐compound phosphors offers significant advantages in color rendering and luminescence efficiency, but their synthesis is challenging because of Eu2+ oxidation. Using the tunable nature of the metal‐ion nodes in metal–organic frameworks (MOFs), we present an in situ reduction and crystallization route for preparing MOFs and doping Eu2+/Eu3+ with a controlled ratio. These materials exhibit rich photoluminescence, including intrinsic‐ and sensitized‐emissions of Eu2+ and Eu3+, and long‐lived luminescence from charge transfer. Color rendering can be easily achieved by fine‐tuning the valence states of Eu. A linear relation between temperature and the intensity ratio of Eu2+/Eu3+ emissions provides outstanding properties for applications as self‐calibrated luminescent thermometers with a wide working temperature range. Further incorporation of Tb3+ into the MOFs results in white light, utilizing all Eu2+,Tb3+, and Eu3+ emissions in a single crystalline lattice.  相似文献   

13.
Series of glass composition (60-x) P2O5 -40 ZnO –(x) Tb2O3 where x = 0.5, 1.0, 1.5, 2.0, 2.5 and 3.0 mol % are prepared by conventional melt quenching technique. X-Ray Diffraction (XRD), FTIR, UV-Vis-NIR and the photoluminescence (PL) spectroscopy are used to characterize the physical, structural and optical behavior of the glass sample. The XRD pattern confirms the amorphous nature and DTA verified the thermal stability of all the glass samples. Glass with 1.5 mol % of Tb2O3 possesses the highest thermal stability. Glass density is found to increase proportionally with increasing amount of Tb3+ while the molar volume behaves reversely. Six main IR absorption bands centered at about 540, 748, 891, 1085 and 1294 cm− 1 are evidenced. The UV-Vis NIR absorption spectra reveals the absorption center band at about 540, 376, 488 and 1920 nm corresponding to the absorption from 7F6 ground state to various excited state of Tb3+ ion. The optical band gaps for direct and indirect transition are in the range 4.53–5.07 eV and 4.30 eV-4.56 eV respectively. The Urbach energy decreases with the increasing concentration of Tb2O3. The PL emission spectra reveals several prominent peaks at 413, 435, 457, 488, 540, 585 and 620 nm due to electronic transition from 5D37F5, 5D37F4, 5D37F3, 5D47F6, 5D47F5, 5D47F3 and 5D47F5 respectively.  相似文献   

14.
Fluorimetry and differential scanning calorimetry have been used to characterize ionomers that were synthesized by copolymerization of methyl methacrylate, methacrylic acid, and europium methacrylate (EMA). Under excitation of UV light at 375 nm no self-quenching was found in fluorescence of EMA-containing ionomers at 615 nm within the Eu3+ concentration range of 1.6 × 10−2 to 11.49 × 10−2 mol %, which means that the distance between two Eu3+ ions is larger than 50 Å. In the same concentration range self-quenching took place in europium octanoate (EOA)-containing ionomers in which EOA was doped as an additive. Only one Tg was found for both kinds of polymers within the concentration range of Eu3+ ions. For all ion contents studied, Tg values were essentially independent of ion content and values were slightly higher for the EMA containing ionomers. © 1997 John Wiley & Sons, Inc.  相似文献   

15.
The luminescence properties of La3TaO4Cl6 are reported and discussed. The rare earth ions Sm3+, Eu3+, Tb3+, Dy3+, and Tm3+ show characteristic absorption and emission lines. For Sm3+ and Eu3+, broad absorption bands are also observed and are attributed to charge-transfer transitions. The line emissions of Tb3+ are only from 5D4, even at low (1 at.%) concentration. Broad excitation and emission bands were observed with In3+. These bands are attributed to In3+Ta5+ → In4+Ta4+ charge-transfer transitions. An additional broad absorption at 250 and 280 nm leading to broad emission at 410 nm is ascribed to OH impurities.  相似文献   

16.
The photoluminescence (PL) studies on NaIn1?xRExW2O8, with RE=Eu3+, Tb3+, Dy3+ and Tm3+ phases have shown that the relative contribution of the host lattice and of the intra-f–f emission of the activators to the PL varies with the nature of the rare earth cation. In the case of Dy3+ and Tm3+ activators, with yellow and blue emission, respectively, the energy transfer from host to the activator plays a major role. In contrast for Eu3+, with intense red emission, the host absorption is less pronounced and the intra-f–f transitions of the Eu3+ ions play a major role, whereas for Tb3+ intra-f–f transitions are only observed, giving rise to green emission.  相似文献   

17.
For the first time, a new langbeinite‐type phosphate, namely potassium terbium tantalum tris(phosphate), K2Tb1.5Ta0.5(PO4)3, has been prepared successfully using a high‐temperature flux method and has been structurally characterized by single‐crystal X‐ray diffraction. The results show that its structure can be described as a three‐dimensional open framework of [Tb1.5Ta0.5(PO4)3] interconnected by K+ ions. The TbIII and TaV cations in the structure are disordered and occupy the same crystallographic sites. The IR spectrum, the UV–Vis spectrum, the morphology and the Eu3+‐activated photoluminescence spectroscopic properties were studied. A series of Eu3+‐doped phosphors, i.e. K2Tb1.5–xTa0.5(PO4)3:xEu3+ (x = 0.01, 0.03, 0.05, 0.07, 0.10), were prepared via a solid‐state reaction and the photoluminescence properties were studied. The results show that under near‐UV excitation, the luminescence colour can be tuned from green through yellow to red by simply adjusting the Eu3+ concentration from 0 to 0.1, because of the efficient Tb3+→Eu3+ energy‐transfer mechanism.  相似文献   

18.
Chitosan membranes with trivalent lanthanide ion Eu3 + were prepared at a ratio of 3:1 w/w (chitosan:lanthanide). There was no membrane formation at a ratio of 1:1 w/w (chitosan: Eu3 + or Tb3 +); in this case a white solid powder was obtained. Both chitosan compounds were characterized by elemental analysis (CHN), thermal analysis (TG/DTG), scanning electron microscopy (SEM) and luminescence spectroscopy. CHN analysis was performed only for chitosan compounds in powder form, suggesting that these compounds have the general formula QUILn.6H2O, where QUI = Chitosan and Ln = Eu3 + or Tb3 +. The results of TG/DTG curves for chitosan membranes with Eu3 + ion indicate that the introduction of this metal into the chitosan structure causes gradual degradation in residual carbons, showing lower weight loss in the Eu3 + membranes compared to pure chitosan membrane. Analysis of luminescence demonstrated that chitosan membranes with Eu3 + ion exhibit emission in the visible region, showing emission bands from chitosan and Eu3 + moieties. For chitosan with Eu3 + and Tb3 + ions compounds, in powder form, the analysis of luminescence suggested that chitosan is not transferring energy to the lanthanide ion; however, the chemical region where the lanthanide ion is found breaks the selection rules and favors the emission of these ions.  相似文献   

19.
Uniform shuttle-like Ln3+ (Eu3+, Tb3+) doped NaLa(WO4)2 nanocrystals have been solvothermally synthesized, and the size of the nanocrystals could be easily controlled by adjusting the volume ratio of ethylene glycol (EG) to water. Doped with 5 mol% Eu3+ and Tb3+ ions, the NaLa(WO4)2 nanocrystals showed strong red and green emissions with lifetimes of 0.8 and 1.40 ms, respectively. A high quenching concentration of 15 mol% was observed in Eu3+-doped NaLa(WO4)2 nanocrystals and 35 mol% in Tb3+-doped NaLa(WO4)2 nanocrystals. The emission intensity measurements of Eu3+-doped NaLa(WO4)2 with different sizes indicated that the emission intensity of shuttles with length of 300 nm in average was stronger than that of shuttles with length of 900 nm in average, but was weaker than that of needles with length of 4 and 9 μm in average.  相似文献   

20.
采用液相法成功制备了MWCNTs负载NaGdF4:Tb3+,Eu3+纳米粒子的磁光热多功能复合纳米材料,并用XRD,SEM和EDS对其结构、组成和形貌进行了表征,结果表明:NaGdF4:Tb3+,Eu3+纳米粒子为六方晶相,形貌为球形且尺寸分布均匀,直径大约为25 nm,并且均匀的包覆在MWCNTs的表面;通过PL,VSM和HTC对复合纳米材料的发光性能,磁性能和光热转换性能进行了表征,采用MTT法对多功能复合纳米材料的生物相容性进行了评估,结果表明:MWCNTs-NaGdF4:Tb3+,Eu3+复合纳米材料具有良好的多色发光性能、磁性能、光热转换性能、低的毒性和良好的生物相容性。该种磁光热多功能复合纳米材料在生物标记、生物成像、肿瘤诊疗等领域有着广泛的应用前景。  相似文献   

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