Judd-Ofelt光谱分析理论

对Judd- Ofelt光谱分析理论 (J- O理论 )的发展和应用进行了综述。J O理论用于分析固体中的稀土离子的吸收、发射光谱 ,可计算它们的跃迁几率、谱线强度、能级寿命、发射截面等。在J O理论中考虑J混合后 ,可使理论和实验结果更好地吻合。采用改进的J -O理论 ,可较好地对Pr3 + 光谱进行分析。由TPM方法 ,可用非极化光透射光谱来分析各向异性晶体的光谱性质 ,并且对样品的加工无特殊定向要求。对于重叠吸收光谱带 ,拟合J- O参数时可以近似为一个带进行处理。利用荧光寿命也可对J- O参数进行计算。

稀土铒离子掺杂的ZrF_2-SiO_2发光性质研究

制备了Er3+掺杂的ZrF2-SiO2材料,测量样品的吸收谱和在980nm LD激发下的上转换荧光发射谱。分析了稀土Er3+中4f电子跃迁的特征,证实了在980 nm泵浦的激发下,ZrF2-SiO2:Er3+ 在404、445 nm和525、548nm附近的蓝/绿可见波段上转换发光过程是激发态吸收(ESA)。

铒/镱掺杂多金属氧酸盐的制备及其近红外发光性研究

制备了高发射率的Keggin结构的铒镱共掺稀土多金属氧酸盐ZnPOM:Er3+,Yb3+,样品在室温980 nm激光激发下具有很强的位于1551nm的近红外发射,共掺样品中镱是铒有效的敏化剂,详细地探讨了镱铒间样品能量传递及近红外发光机理.

Tm^(3+)/Yb^(3+)/Er^(3+)共掺氟氧硅酸盐玻璃的上转换发光特性

利用熔融法制备了Tm3+/Yb3+/Er3+共掺氟氧硅酸盐玻璃.在980nm LD激发下,研究了Tm3+离子和Er3+离子之间的能量传递和Tm3+离子的上转换荧光,分析了Tm3+离子的上转换机理,发现蓝色上转换荧光是三光子过程对应于1 G4→3 H6的跃迁,而红色上转换荧光是双光子过程对应于1 G4→3 F4的跃迁.比较不同掺杂摩尔分数的样品的荧光强度,发现Tm3+离子的最佳掺杂摩尔分数为0.2%.

Er^(3+)掺杂Ge-Ga-S-KBr硫卤玻璃的中红外发光和多声子弛豫的研究

为了获得能输出中红外荧光的理想基质玻璃,用熔融急冷法制备了系列不同Er3+离子掺杂浓度的Ge-Ga-S-KBr硫卤玻璃,测试了样品折射率、吸收光谱、中红外荧光光谱.通过吸收光谱计算了Er3+离子吸收谱线的振子强度,应用Judd-Ofelt理论计算分析了Er3+离子在Ge-Ga-S-KBr硫卤玻璃中的强度参量Ωi(i=2,4,6)、自发辐射跃迁几率A、荧光分支比β等光谱参量.研究了808nm激光抽运下样品中红外荧光特性与掺杂浓度之间变化关系,并用Futchbauer-Ladenburg公式分别计算了2.8μm处的受激发射截面.结果表明,在808nm激光抽运下观察到了2.8μm中红外荧光,对应于Er3+:4I11/2→4I13/2跃迁,当Er3+离子掺杂浓度从0.4wt%增加到1.0wt%时,中红外荧光强度相应增加,计算的Er3+:4I11/2能级的多声子驰豫速率为37s-1.

Y_2O_3:Er^(3+)和Y_2O_3:Er^(3+),Yb^(3+)纳米粉体的制备及上转换发光性能的研究

利用硝酸盐和尿素作为原料通过均相共沉淀法合成了分散性良好的Y_2O_3:Er^(3+)和Y_2O_3:Er^(3+),Yb^(3+)球形纳米粉体,粒径大小分别为100～115 nm和110～145nm.X-射线衍射结果显示,所制备的掺杂粉体仍然保持了立方Y_2O_3的物相结构.在980nm激光的激发下,Y_2O_3:Er^(3+)样品的发光情况随着Er^(3+)离子浓度的增加,上转换红光的发射强度都先增加后减小,而绿光的强度则逐渐减小.究其原因是交叉弛豫2H_(11/2)+~4I_(13/2)→~4I_(9/2)+~4F_(9/2),~4F_(7/2)+~4I_(11/2)→~4F_(9/2)+~4F_(9/2),~2H_(11/2)+~4I_(15/2)→~4I_(9/2)+~4I_(13/2)和~4I_(13/2)+~4I_(11/2)→~4F_(9/2)+~4I_(15/2)的发生.Y_2O_3:Er^(3+),Yb^(3+)则且随着Yb^(3+)离子浓度的提高,上转换红、绿光的发射强度都增加,但上转换红光发射强度增加的幅度明显要大于上转换绿光发射强度增加的幅度.通过调整Yb"离子的掺杂浓度使其发光颜色在绿色、红色之间转变,其中单带红光上转换发光是由于在Yb^(3+)离子掺杂浓度较高时,Er^(3+)离子和Yb^(3+)离子之间发生了能量反向传递.

Er^(3+)及Er^(3+)/Yb^(3+)掺杂ZrO_2-Al_2O_3的制备及发光性质

采用共沉淀法制备了纳米晶ZrO2-Al2O3∶Er3+发光粉体.所制备的粉体室温下具有Er3+离子特征荧光发射,主发射在绿光,其中位于547nm、560nm的绿光最强,并得出稀土离子与基质之间有能量传递.对不同煅烧温度下的样品研究表明:因不同温度下所制得的样品晶相不同.研究了纳米晶ZrO2-Al2O3∶Er3+及ZrO2-Al2O3∶Er3+/Yb3+的上转换发光,并分析了上转换的跃迁机制.发现ZrO2-Al2O3∶Er3+的绿光为双光子过程,而ZrO2-Al2O3∶Er3+、Yb3+的上转换光谱中,红光和绿光也为双光子过程,而极弱的蓝光为三光子过程.讨论了Er3+的浓度猝灭现象.最适宜掺杂浓度的原子分数为2%(Er3+/Zr4+).

NaYF_4∶Yb^(3+),Er^(3+)纳米粒子的上转换发光的温度特性

利用高温热溶剂法合成了NaYF4∶20%Yb3+,2%Er3+纳米粒子,通过X射线衍射谱、扫描电镜及低温荧光光谱对其结构、形貌及发光性质进行了表征。研究结果表明:合成的纳米粒子为六角相,粒径大小约30nm。变温光谱研究表明:由于4S3/2和2H11/2能级差较小,当温度增加至45 K时,4S3/2能级和2H11/2能级的电子布局同时相应地增加;而当温度超过45 K之后,温度依赖的2H11/2能级布局随着温度的提高而增多,表现为520 nm的发光随着温度的提高一直增强。由于无辐射弛豫速率随温度升高而快速增加,导致545 nm的发光随着温度的提高先增强后减弱。

Fabrication and Luminescence Properties of Ca_2Gd_8 (SiO_4 )_6O_2:Er^(3+) Phosphors via Sol-Gel Process

Ca2RE8(SiO4)6O2(RE = Y, Gd, La) is a kind of ternary rare-earth-metal silicate with the oxyapatite structure, which was used as host materials for the luminescence of various rare earth and mercury-like ions. Ca2Gd8(SiO4)6O2: Er3 + phosphors were prepared through the sol-gel process. X-ray diffraction (XRD), scanning electron microscopy (SEM) and photoluminescence spectra were used to characterize the resulting phosphors. The results of XRD indicate that the phosphors crystallized completely at 1000℃. SEM study reveals that the average grain size is 400 ~ 1000 nm. In Ca2Gd8 (SiO4)6O2 : Er3+ phosphors, the Er3+ shows its characteristic green emission at 528 nm (2H11/2-4I15/2) and 548 nm (4 S3/2-4 I15/2) upon excitation into 382 nm, with an optimum doping concentration of 5% (mole fraction) of Gd3+ in the host lattices.

980 nm半导体激光器激发下Er^(3+),Yb^(3+)共掺杂氟氧化物微晶玻璃的上转换发光

测量了Ｅｒ３＋，Ｙｂ３＋掺杂氟氧化物微晶玻璃的吸收光谱、激发光谱、上转换发光光谱及其强度随泵浦光强的变化，讨论了其上转换发光特性．

Research on Up-Conversion Mechanism in Er^(3+)/Yb^(3+)-Codoped Oxyfluoride Glass

Er3 +/Yb3 +-codoped oxyfluoride crystallite glass was prepared with melting technique. The compositions and the melting temperature and the annealing temperature of the rare earth-doped crystallite glass were studied in detail. The emission spectra of samples were measured with the Hitachi F-4500 fluorescent photometer pumped by 980 nm wavelength laser. The up-conversion luminescence mechanism was illuminated on the view of the photophysics. By measuring the relationship between luminescent intensity and pump power, it is confirmed that the emission peaks at 550 nm belong to two-photon process, while that at 665 nm belongs to three-photon process. Moreover, the distributions of crystalline were determined by SEM.

Phase-, shape- and size-controlled synthesis of NaYF_4:Yb^(3+),Er^(3+) nanoparticles using rare-earth acetate precursors

Hexagonal-phase NaYF4：Yb3＋,Er3＋ upconversion nanoparticles（UCNPs） with a uniform size distribution were synthesized using rare-earth acetates as precursors. The effects of reaction temperature and time on the phase transition process of the UCNPs were systematically studied. Based on the evolution of particle morphology and phase with temperature and time, it could be concluded that the transition from cubic phase to hexagonal phase for NaYF4：Yb3＋,Er3＋ UCNPs was consistent with a dissolution/recrystallization process. In addition, the shape and size of the UCNPs could be controlled by adjusting the solvent ratio and the precursor ratio, respectively.

Upconversion Emission in Er^(3+) Doped Novel Bismuthate Glass

Novel Er3+-doped bismuth lead strontiam glass was fabricated and characterized, and the absorption spectrum and upconversion spectrum of the glass were studied. The Judd-Ofelt intensity parameters Ωt (t=2, 4, 6) were found to be Ω2=3.27×10-20 cm2, Ω4=1.15×10-20 cm2, and Ω6=0.38×10-20 cm2. The oscillator strength, the spontaneous transition probabilities, the fluorescence branching ratios, and excited state lifetimes were also measured and calculated. The upconversion emission intensity varies with the power of infrared excitation intensity. A plot of log Iup vs log IIR yields a straight line with slope 1.86, 1.88 and 1.85, corresponding to 525, 546, and 657 nm emission bands, respectively, which indicates that a two-photon process for the red and green emission.

Covalent bonding and J–J mixing effects on the EPR parameters of Er^(3+) ions in GaN crystal

The EPR parameters of trivalent Er（3＋） ions doped in hexagonal Ga N crystal have been studied by diagonalizing the 364×364 complete energy matrices. The results indicate that the resonance ground states may be derived from the Kramers doublet Γ6. The EPR g-factors may be ascribed to the stronger covalent bonding and nephelauxetic effects compared with other rare-earth doped complexes, as a result of the mismatch of ionic radii of the impurity Er（3＋）ion and the replaced Ga（3＋） ion apart from the intrinsic covalency of host Ga N. Furthermore, the J–J mixing effects on the EPR parameters from the high-lying manifolds have been evaluated. It is found that the dominant J–J mixing contribution is from the manifold 2K（15/2）, which accounts for about 2.5%. The next important J–J contribution arises from the crystal–field mixture between the ground state 4I（15/2） and the first excited state4I（13/2）, and is usually less than 0.2%. The contributions from the rest states may be ignored.

Site Selective Excitation and Energy Transfer in LiKGdF_5 Crystal Co-doped with Er^(3+) and Tb (3+)

Crystals of LiKGdF 5∶Er 3+, Tb 3+ grown by the hydrothermal synthesis technique with concentrations of 2% and 0.4% were analysed. By using site selective excitation measured at low temperature, luminescence and excitation spectra from Er 3+ and Tb 3+ ions embedded in LiKGdF 5 were clearly separated. The lifetimes of the emitting levels 4S 3/2 of Er 3+ and 5D 4 of Tb 3+ were also determined. Following the site selective spectroscopy study, the dominant energy transfer process from Tb 3+ to Er 3+ in the crystal was then investigated via transient experiments.

Optical Properties of a Novel Trivalent Erbium Ions Doped into Phosphate Glass

A novel Er (3+)-doped (ZnO)(P_2O_5)(B_2O_3) glass with excellent optical properties was prepared. The glasses were proved to have high stability by the investigation of the durability in boiling water. The properties of their spectra at about 1.5 μm change a lot with the concentrations of both Er (3+) and B_2O_3. Compared with Er (3+)-doped into the borate glass and the zinc phosphate glass,the glass prepared in our laboratory shows a larger quenching concentration and a much broader emission band at 1.54 μm.

Effect of Li＋ ion concentration on upconversion emission and temperature sensing behavior of La2O3：Er3＋ phosphors

The effects of Li~＋ co-doping concentration on the structure, upconversion luminescence and temperature sensing behavior of Er^（3＋）：La_2O_3 phosphors were investigated. X-ray diffraction and scanning electron microscopy observations reveal that Li~＋ ion co-doping can change the lattice parameter of La_2O_3 host and increase the particle size of the samples. The optical investigation shows that co-doping of Li~＋ ions can enhance the upconversion emission of Er^（3＋） ions in La_2O_3 matrix effectively. Most importantly, the temperature sensing sensitivity of the samples is found to be dependent on Li~＋ co-doping concentration,when the emission intensity ratio of the（~2H_（11/2）→~4 I_（15/2）） and（~4 S_（3/2）→~4 I_（15/2）） transitions of Er^（3＋） is chosen as the thermometric index. Both of the optimum upconversion luminescence and temperature sensing sensitivity are obtained for 7 mol% Li~＋ co-doped sample. When the Li~＋ concentration is beyond 7 mol%,both the quenching in upconversion intensity and the degradation of temperature sensitivity are observed, which may be due to the serious distortion in local crystal field around Er^（3＋） ions caused by the excess Li~＋ ions.

Synthesis and characterization of NaYF4:Yb3+,Er3+@silica-N=folic acid nanocomplex for bioimaginable detecting MCF-7 breast cancer cells

Upconversion nanophosphors are new promising nanomaterials to be used as biolabels for detection and imaging of cancer cells.These nanophosphors absorb long-wavelength excitation radiation in the infrared or near infrared region and emit shorter wavelength,higher energy radiation from ultraviolet to infrared.In this paper,we studied the hydrothermal method and optical properties of the functionalized NaYF4:Yb^3+,Er^3+for biomedical application.After synthesis,these NaYF4:Yb^3+,Er^3+nanophosphors were functionalized with aminosilanes and folic acid.Folic acid binds to the folate receptor on the surface of MCF-7 breast cancer cells and this binding promotes internalization of the nanophosphors via endocytosis.The sizes of the functionalized NaYF4:Yb^3+,Er^3+@silica-N=FA(folic acid)nanophosphors can be controlled with length of the rod about 300-800 nm and diameter of the rod about 100-200 nm.Phase structure of NaYF4:Yb^3+,Er^3+is in hexagonal crystal system.The photo luminescence(PL)spectra of the functionalized NaYF4:Yb^3+,Er^3+@silica-N=FA nanophosphors were measured.These nanophosphors emit in red color with the strongest band at 650 nm under 980 nm excitation.This result can provide NaYF4:Er^3+,Yb^3+@silica-N=FA complex for developing fluorescence label and image tool in cancer biology and medicine.

Upconversion luminescence of Gd2O3:Er3+and Gd2O3:Er3+/silica nanophosphors fabricated by EDTA combustion method

Gd2O3:Er^3+nanophosphors were fabricated by the combustion method in presence of Na2 ethylene diamine tetra acetic acid(EDTA-Na2)as fuel at not high temperature(≤350℃)within a very short time of 5 min.The added concentration of Er^3+ions in Gd2O3 matrix was changed from 0.5 mol%to 5.0 mol%.The X-ray diffraction pattern of samples indicates the monoclinic structure of Gd2O3:Er^3+.The morphology and chemical composition analysis of the Gd2O3:Er^3+samples are characterized by a field emission scanning electron microscope(FESEM)and a Fourier-transform infrared spectrometer(FTIR).The photoluminescence(PL),photo luminescence excitation(PLE)and upconversion(UC)at room temperature of the prepared materials with different concentrations of Er^3+were investigated.The PL of Gd2O3:Er^3+nanomaterials are shown in visible at 545,594,623,648,688 nm under excitation at 275 nm.The emission bands from transitions of Er^3+from 2P3/2 to 4F9/2 are observed,UC luminescent spectra of the Gd2O3:Er^3+/silica nanocomposites under 976 nm excitation show the bands at 548 and 670 nm.The influence of excitation power at 980 nm for transitions were measured and calculated.The results indicate that the upconversion process of Gd2O3:Er^3+/silica is two photons absorption mechanism.The low temperature dependence of UC luminescent intensities of the main bands of Gd2O3:Er^3+was investigated towards development of a nanotemperature sensor in the range of 10-300 K.

Upconversion luminescence of Y2Ti2O7：Er3＋ under 1550 and 980 nm excitation

Er^（3＋） doped Y_2Ti_2O_7 phosphors were prepared by the high temperature solid state reaction method at 1500℃.X-ray diffraction and luminescence spectra were used to characterize the properties of samples.Due to the layer distribution of Y^（3＋） ions in the pyrochlore Y_2Ti_2O_7 crystal,Er^（3＋） ions,replacing Y^（3＋） in Y_2Ti_2O_7 crystal,could realize high-concentration doping by suppressing energy migration between layers to minimize concentration quenching.Investigation on the upconversion characteristic of Y_2Ti_2O_7：Er^（3＋）showed that the optimal doping concentration of Er^（3＋） was up to 28 mol.%.Y_2Ti_2O_7：0.28 Er^（3＋） exhibited both dominating red emission under 980 and 1550 nm excitation.The brightness of Y_2Ti_2O_7：0.28Er^（3＋） were 4 times（980 nm） and 7 times（1550 nm） higher than that of Y_2Ti_2O_7：0.05Er^（3＋）.And Y_2Ti_2O_7：Er^（3＋） presented much better red emission color purity and stability under 1550 nm excitation.