Yb3+/Tm3+掺杂的NaY(WO4)2纳米晶的制备及发光特性

以聚乙二醇为配位剂,用水热法制备出纳米级上转换发光粉Yb3+和Tm3+共掺杂的NaY(WO4)2。研究了不同cYb/cTm对上转换发光强度的影响,实验表明当cYb/cTm=5∶1时,上转换发光强度最强。用XRD,SEM确定了Yb3+和Tm3+共掺杂的NaY(WO4)2是四方晶系,其粒径在25~35 nm范围,且分散均匀。用980 nm半导体激光器(LD)对其进行激发,在室温下观察到了365 nm附近紫外发射峰、456 nm,476 nm附近的蓝光发射峰和648 nm附近的红光发射峰,分别对应于Tm3+离子的1D2→3H6,1D2→3F4,1G4→3H6和1G4→3F4的跃迁。根据泵浦功率与发光强度的关系得出紫外发射峰、蓝光和红光发射均为双光子过程。     

Luminescence Properties and Crystal Growth of Er/Yb Codoped KGd（WO4）2

1 INTRODUCTION In recent years much interest has been shown in the radiation laser around 1.54 μm for optical com- munications, medical and eye-safe light detecting and ranging applications[1～3]. Emission in the 1.54 μm range can be achieved with Er3 ion through 4I13/2→4I15/2, but the LD-pumping laser efficiency is commonly low owing to the weak absorption in- tensity of Er3 ion. Yb3 ion is often used as a sen- sitizer ion to increase the absorption light and then transfer the en…     

Highly uniform and monodisperse beta-NaYF(4):Ln(3+) (Ln = Eu, Tb, Yb/Er, and Yb/Tm) hexagonal microprism crystals: hydrothermal synthesis and luminescent properties

beta-NaYF4:Ln3+ (Ln = Eu, Tb, Yb/Er, and Yb/Tm) hexagonal microprisms with remarkably uniform morphology and size have been synthesized via a facile hydrothermal route. X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), high-resolution transmission electron microscopy (HRTEM), and photoluminescence (PL) spectra as well as kinetic decays were used to characterize the samples. It is found that sodium citrate as a shape modifier introduced into the reaction system plays a critical role in the shape evolution of the final products. Furthermore, the shape and size of the products can be further manipulated by adjusting the molar ratio of citrate/RE3+ (RE represents the total amount of Y3+ and the doped rare earth elements such as Eu3+, Tb3+, Yb3+/Er3+, or Yb3+/Tm3+). Under the excitation of 397 nm ultraviolet light, NaYF4:xEu3+ (x = 1.5, 5%) shows the emission lines of Eu3+ corresponding to 5D0-3 --> 7FJ (J = 0-4) transitions from 400 to 700 nm (whole visible spectral region) with different intensity, resulting in yellow and red down-conversion (DC) light emissions, respectively. When doped with 5% Tb3+ ions, the strong DC fluorescence corresponding to 5D4 --> 7FJ (J = 6, 5, 4, 3) transitions with 5D4 --> 7F5 (green emission at 544 nm) being the most prominent group that has been observed. In addition, under 980 nm laser excitation, the Yb3+/Er3+- and Yb3+/Tm3+-codoped beta-NaYF4 samples exhibit bright green and whitish blue up-conversion (UC) luminescence, respectively. The luminescence mechanisms for the doped lanthanide ions were thoroughly analyzed.     

Optical spectroscopy of Yb(3)Al(5)O(12) single crystal

Yb(3)Al(5)O(12) single crystal has been grown by Czochralski (CZ) method. The absorption spectrum was investigated at low temperature and the electronic energy levels for (2)F(5/2) multiplet of Yb(3+) in YbAG was proposed. The up-conversion emission of the crystal under 940 nm diode pumping and the X-ray excited luminescence (XEL) features of the crystal were also studied.     

Yb:Er:Tm:LiTaO3的上转换发白光性能研究

980 nm脉冲激光激发下,首次通过高温固相法制备Yb(10%):Er(1%):Tm(1%):LiTaO3(摩尔分数)多晶粉并实现室温上转换白光.X射线粉末衍射测试结果表明,Yb:Er:Tm:LiTaO3中的掺杂离子并没有改变晶格结构,以取代的方式存在于钽酸锂晶格中.结合功率曲线测试结果和上转换机制研究发现,产生上转换蓝光的Tm3+离子1G4态的布居主要来自双光子同时吸收过程.而单光子上转换输出的红光,则由Tm3+和Er3+离子之间的交叉弛豫过程产生,即3F2/3(Tm3+)+4I15/2(Er3+)→3H6(Tm3+)+4I9/2(Er3+).上转换绿光来源于Yb/Er离子对的二次能量传递.     

MgAl2O4∶Er^3+,Yb^3+荧光粉的制备及其上转换发光性能

以尿素为沉淀剂,采用低温水热法结合煅烧过程制备出MgAl2O4∶Er^3+,Yb^3+上转换荧光粉,并对样品的结构、微观形貌及上转换发光性能予以表征。结果表明,随尿素加入量的增大,产物主形貌由六角片状结构向纳米棒状转变,经1100℃煅烧可得纯相镁铝尖晶石结构,且Er^3+和Yb^3+能有效进入MgAl2O4晶格并占据Mg^2+位置形成均匀固溶体。在980 nm光激发下,MgAl2O4∶1.0%(n/n)Er^3+,x%(n/n)Yb^3+(x=0~8.0)荧光粉表现出在524、545 nm处绿光以及658 nm处的强红光发射,红绿光强度均在5.0%(n/n)Yb^3+掺杂时达到最大,但红绿光强度比却在7.0%(n/n)Yb^3+掺杂时达到最大值5.2,这归因于Er^3+-Er^3+之间交叉弛豫(CR)在红光发射过程中所起的重要作用。通过控制荧光粉中Yb^3+的掺杂量,能初步实现对于黄绿光色度的有效调控。     

Ca3Al2Ge3O12:Cr3+的光谱性质及晶场参数计算

为了解Cr3+离子在钙铝锗酸盐Ca₃Al₂Ge₃O₁₂:石榴石中的光谱性质, 合成了Ca₃Al₂Ge₃O₁₂:Cr³⁺多晶材料；测量了其X射线衍射图, 漫反射光谱, 激发、发射光谱等；分析了Cr3+离子在钙铝锗酸盐中的发光特性；计算了其晶场强度(Dq/B), Stokes位移(ΔEs)及黄昆-里斯因子(S)等. 在450 nm激发下, Ca₃Al₂Ge₃O₁₂:Cr³⁺室温发射光谱主要由三个宽带及附加其上的弱R线构成, 分别对应于Cr3+离子的4T1、 4T2、2T2到 4A2 能级跃迁. 低温时R线变得强而锐. 通过计算, Dq/B=2.43, ΔEs=1884 cm-1, S=5.21. 表明在Ca₃Al₂Ge₃O₁₂中Cr³⁺离子处于较弱的晶场强度, 电子-声子耦合较强, 为发展可调谐激光材料提供重要线索.     

Growth and Spectroscopic Characteristics of Yb3＋：LiGd（WO4）2 Crystal

The Yb3+:LiGd(WO4)2 crystal with the dimension of Φ15×35 mm3 was grown by Czochralski technique. The spectroscopic characterization and fluorescence dynamics of Yb3+ in Yb3+:LiGd(WO4)2 crystal were investigated. The Yb3+:LiGd(WO4)2 crystal exhibits a broad absorption band centered near 975 nm with the linewidths of 16 and 11 nm and maximal absorption cross-section of 3.60 × 10-20 and 2.90 × 10-20 cm2 for π- and σ-polarization, respectively. The emission broadband has an FWHM of 47 and 45 nm with the emission cross sections of 3.92 × 10-20 and 3.34 × 10-20 cm2 at 1020 nm for π- and σ-polarization, respectively. The measured fluorescence lifetime is 398 μs. The blue light emission around 480 nm through cooperative upconversion from the de-excitation of excited Yb3+-Yb3+ pairs at 4 K was observed under 932-nm excitation and demonstrated.     

Sensitive and selective PET-based diimidazole luminophore for Zn(II) ions: a structure-activity correlation

3-(3-Ethoxymethyl-1H-imidazol-2-yl)-3-(1-ethoxymethyl-1H-imidazol-2-yl)-3H-benzo[de]isochromen-1-one, 4, is a novel photoinduced electron transfer (PET) chemosensor that becomes fluorescent upon binding metal ions and shows a strong preference toward Zn(II) ions. The new bisimidazol PET sensor and its zinc complex were prepared and characterized in terms of their crystal structures, absorption and emission spectra, and orbital energy diagrams. Free 4 is a weakly luminescent species. On the basis of detailed DFT calculations, we suggest that the poor luminescence yield of free 4 originates from its orbital structure in which two pi-orbitals of the two imidazole rings, HOMO and HOMO-1, are situated between two pi-orbitals of the isochromene-one system, HOMO-2 and LUMO. The absorption and emission processes occur between the two pi-orbitals of the isochromene-one system, HOMO-2 and LUMO, and the two pi-imidazole orbitals serve as quenchers for the excited state of the molecule through nonradiative processes. Upon binding Zn(II) ions, 4 becomes a highly luminescent species having a luminescence maximum peaking at 375 nm (lambda(ex) = 329 nm). The significant 900-fold enhancement in luminescence upon binding of the Zn(II) ions is attributed to the stabilization of the pi-orbitals of the imidazole rings upon their engagement in new bonds with the zinc ion. The affinity of 4 to zinc ions in acetonitrile is found to be very high, Ka > 3 x 10(6) M(-1), while with other metals ions, the association constants are considerably weaker.     

Silica-coated Ln3+-Doped LaF3 nanoparticles as robust down- and upconverting biolabels

The preparation of nearly monodisperse (40 nm), silica-coated LaF(3):Ln(3+) nanoparticles and their bioconjugation to FITC-avidin (FITC=fluorescein isothiocyanate) is described in this report. Doping of the LaF(3) core with selected luminescent Ln(3+) ions allows the particles to display a range of emission lines from the visible to the near-infrared region (lambda=450-1650 nm). First, the use of Tb(3+) and Eu(3+) ions resulted in green (lambda=541 nm) and red (lambda=591 and 612 nm) emissions, respectively, by energy downconversion processes. Second, the use of Nd(3+) gave emission lines at lambda=870, 1070 and 1350 nm and Er(3+) gave an emission line at lambda=1540 nm by energy downconversion processes. Additionally, the Er(3+) ions gave green and red emissions and Tm(3+) ions gave an emission at lambda=800 nm by upconversion processes when codoped with Yb(3+) (lambda(ex)=980 nm). Bioconjugation of avidin, which has a bound fluorophore (FITC) as the reporter, was carried out by means of surface modification of the silica particles with 3-aminopropyltrimethoxysilane, followed by reaction with the biotin-N-hydroxysuccinimide activated ester to form an amide bond, imparting biological activity to the particles. A 25-fold or better increase in the FITC signal relative to the non-biotinylated silica particles indicated that there is minimal nonspecific binding of FITC-avidin to the silica particles.     

Study of upconversion fluorescence property of novel Er3+/Yb3+ co-doped tellurite glasses

Er3+/Yb3+ co-doped TeO2-B2O3-Nb2O5-ZnO (TBN) glasses were prepared. The absorption spectra and upconversion luminescence spectra of TBN glasses were measured and analyzed. The upconversion emission bands centered at 530, 546 and 658 nm were observed under the excitation at 975 nm, corresponding to the transitions of 2H11/2-->4I15/2, 4S3/2-->4I15/2 and 4F9/2-->4I15/2 respectively. The ratio of red emission to green emission increases with an increasing of Yb3+ ions concentration. According to the quadratic dependence on excitation power, the possible upconversion mechanisms and processes were discussed.     

Strong green emission from alpha-SiAlON activated by divalent ytterbium under blue light irradiation

This contribution reports on luminescence properties of divalent ytterbium in alpha-SiAlON at room temperature. Ytterbium-doped alpha-SiAlON powders, with the compositions of (M(1-2x/v)Yb(x))(m/v)Si(12-m-n)Al(m+n)O(n)N(16-n) (M = Ca, Li, Mg, and Y, v is the valency of M, 0.002 < or = x < or = 0.10, 0.5 < or = m = 2n < or = 3.5), were synthesized by sintering at 1700 degrees C for 2 h under 0.5 MPa N2. A single, intense, broad emission band, centered at 549 nm, is observed due to the electronic transitions from the excited state 4f(13)5d to the ground state 4f14 of Yb2+. The luminescence of Yb2+ in alpha-SiAlON occurs at relatively low energy, which is attributable to the large crystal field splitting and nephelauxetic effect due to the nitrogen-rich coordination of Yb2+. The dependence of luminescence properties on the Yb2+ concentration, chemical composition, and annealing is discussed. It is suggested that this novel green phosphor could be applied in white light-emitting diodes (LEDs) when combined with a red phosphor and a blue LED.     

Fluorescence investigation of Ho3+ in Yb3+ sensitized mixed-alkali bismuth gallate glasses

Efficient 2.0 microm infrared and visible upconversion emissions have been observed in Ho3+/Yb3+ co-doped mixed-alkali bismuth gallate (LKBBG) glasses having a maximum-phonon energy of 673 cm(-1). The Judd-Ofelt parameters Omega2, Omega4 and Omega6 of Ho3+ indicate that there is a high asymmetry and strong covalent environment in LKBBG glasses. The large absorption and emission cross-sections of Yb3+ confirm that it is a suitable sensitizer for capturing and transferring pump energy to Ho3+. The emission cross-section profile for the 5I7-->5I8 transition is derived using the reciprocity method and the peak value is 5.54 x 10(-21)cm2, which is much larger than the value in fluorozircoaluminate glasses. LKBBG glasses exhibit low maximum-phonon energy and large refractive index, and it is possible to achieve an effective 1.66 microm U-band emission of Ho3+ under 900 nm laser radiation.     

Optical transitions of Er3+/Yb3+ codoped TeO2-WO3-Bi2O3 glass

Optical absorption and emission properties of the Er3+/Yb3+ codoped TeO2-WO3-Bi2O3 (TWB) glass has been investigated. The transition probabilities, excited state lifetimes, and the branching ratios have been predicted for Er3+ based on the Judd-Ofelt theory. The broad 1.5 microm fluorescence was observed under 970 nm excitation, and its full width at half maximum (FWHM) is 77 nm. The emission cross-section is calculated using the McCumber theory, and the peak emission cross-section is 1.03 x 10(-21) cm2 at 1.531 microm. This value is much larger than those of the silicate and phosphate glasses. Efficient green and weak red upconversion luminescence from Er3+ centers in the glass sample was observed at room temperature, and the upconversion excitation processes have been analyzed.     

Strong visible up-conversion emission in Tb3+, Tm3+ and Tb3+-Tm3+ co-doped tellurite glasses sensitized by Yb3+

Up-conversion luminescence characteristics under 975 nm excitation have been investigated with Tb3+/Tm3+/Yb3+ triply doped tellurite glasses. Here, green (547 nm: (5)D(4)-->(7)F(4)) and red (660 nm: (5)D(4)-->(7)F(2)) up-conversion (UC) luminescence originating from Tb3+ is observed strongly, because of the quadratic dependences of emission intensities on the excitation power. Especially, the UC luminescence was intensified violently with the energy transfer from the Tm3+ ions involves in the Tb3+ excitation. To the Tb3+/Tm3+/Yb3+ triply doped glass system, a novel up-conversion mechanism is proposed as follows: the energy of (3)G(4) level (Tm3+) was transferred to (5)D(4) (Tb(3+)) and the 477-nm UC luminescence of Tm3+ was nearly quenched.     

Growth and Spectroscopic Properties of Nd3＋：Sr3Gd2（BO3）4 Crystal

<正>This paper reports the growth,X-ray diffraction and spectroscopy of Nd~(3+):Sr_3Gd_2(BO_3)_4 crystal.A Nd~(3+):Sr_3Gd_2(BO_3)_4 crystal with dimensions ofφ20×45 mm~3 has been grown by the Czochralski method.Nd~(3+):Sr_3Gd_2(BO_3)_4 crystal belongs to the orthorhombic system,space group Pnma(D_(2h))with a=0.7401,b=1.604 and c=0.8755 nm.The absorption and emission spectra of Nd~(3+):Sr_3Gd_2(BO_3)_4 were investigated.The absorption cross sectionσ_a is 3.11×10~(-20)cm~2 at 808 nm. The absorption transition at 808 nm has an FWHM of 14 nm.The luminescence lifetimeτ_f is 51.7 us.The emission cross sectionσ_e at 1064 nm wavelength is 1.09×10~(-19)cm~2.     

Cooperative near-IR to visible photon upconversion in Yb3+-doped MnCl2 and MnBr2: comparison with a series of Yb3+-doped Mn2+ halides

Yb3+-doped MnCl2 and MnBr2 crystals exhibit strong red upconversion luminescence under near-infrared excitation around 10 000 cm(-1) at temperatures below 100 K. The broad red luminescence band is centred around 15 200 cm(-1) for both compounds and identified as the Mn2+ 4T1g-->6A1g transition. Excitation with 10 ns pulses indicates that the upconversion process consists of a sequence of ground-state and excited-state absorption steps. The experimental VIS/NIR photon ratio at 12 K for an excitation power of 191 mW focused on the sample with a 53 mm lens is 4.1% for MnCl2:Yb3+ and 1.2% for MnBr2:Yb3+. An upconversion mechanism based on exchange coupled Yb3+-Mn2+ ions is proposed. Similar upconversion properties have been reported for RbMnCl3:Yb3+, CsMnCl3:Yb3+, CsMnBr3:Yb3+, RbMnBr3:Yb3+, Rb2MnCl4:Yb3+. The efficiency of the upconversion process in these compounds is strongly dependent on the connectivity between the Yb3+ and Mn2+ ions. The VIS/NIR photon ratio decreases by three orders of magnitude along the series of corner-sharing Yb3+-Cl--Mn2+, edge-sharing Yb3+-(Cl-)2-Mn2+ to face-sharing Yb3+-(Br-)3-Mn2+ bridging geometry. This trend is discussed in terms of the dependence of the relevant super-exchange pathways on the Yb(3+)-Mn2+ bridging geometry.     

Cooperative energy transfer frequency upconversion in Tb3+/Yb3+-codoped oxyfluoride glasses

In this report, we investigate the cooperative energy transfer frequency upconversion in Tb3+/Yb3+-codoped SiO2-Al(2)O(3)-Na2O-ZnF(2) oxyfluoride glasses under 980 nm diode laser excitation. The influence of both Tb3+ and Yb3+ concentration on the emission bands were investigated. With a lower Tb3+ concentration, the emission bands around 381, 416 and 438 nm, and 489, 545, 587 and 623 nm associated with (5)D(3), (5)G(6)-->(7)F(J) (J=6, 5, 4) and (5)D(4)-->(7)F(J) (J=6, 5, 4, 3) transitions were observed. However, only (5)D(4)-->(7)F(J) (J=6, 5, 4, 3) transitions appear in a higher Tb3+ concentration. The integrated upconversion luminescence intensity was examined when the temperature of sample was varied from 40 to 450 K. The dependence of the upconversion emission intensity upon the excitation power was also examined, and the upconversion mechanisms were discussed.     

绿色荧光粉Ba2-xB2O5:xTb3+的制备及发光性能研究

采用高温固相法合成了Ba2-xB2O5:xTb3+绿色荧光粉。XRD图谱表明合成物质为纯相的Ba2B2O5晶体。该样品在256 nm(4f8→4f75d1)处有最强激发;有4个发射峰,分别位于489 nm(5D4→7F6),545 nm(5D4→7F5),585 nm(5D4→7F4)和622 nm(5D4→7F3);其中在545 nm处有最强发射。随着Tb3+掺杂浓度的不同,激发峰与发射峰的强度先增大后减小,当x=0.7时最佳。研究了电荷补偿剂Na+对发光性能的影响,样品的发射光谱强度随Na+掺杂浓度的增大而增大,当掺杂浓度达到或超过Tb3+浓度后发射光谱强度下降。     

Optical spectroscopy of lanthanide ions in ZnO-TeO2 glasses

Zinc tellurite glasses of compositions 19ZnO-80TeO2-1Ln2O3 with Ln = Eu, Er, Nd and Tm were prepared by melt quenching. The absorption spectra were measured and from the experimental oscillator strengths of the f-->f transitions the Judd-Ofelt parameters ohm(lambda) were obtained. The values of the ohm(lambda) parameters are in the range usually observed for oxide glasses. For Nd3+ and Er3+, luminescence spectra in the near infrared were measured and the stimulated emission cross sections sigma(p) were evaluated for some laser transitions. The high values of sigma(p), especially for Nd3+, make them possible candidates for optical applications. Fluorescence line narrowing (FLN) spectra of the Eu3+ doped glass were measured at 20 K, and the energies of the Stark components of the 7F1 and 7F2 states were obtained. A crystal field analysis was carried out assuming a C2v site symmetry. The behaviour of the crystal field ratios B22/B20 and B44/B40 agrees reasonably well with the values calculated using the geometric model proposed by Brecher and Riseberg. The crystal field strength at the Eu3+ sites appears to be very low compared to other oxide glasses.