YAG:Yb~(3+),Tm~(3+)纳米晶粉体的制备及其蓝色上转换发光

以稀土氧化物、硝酸铝为原料,采用溶胶-凝胶法合成了Yb3+、Tm3+共掺的钇铝石榴石(Y3Al5O12,YAG)纳米晶粉体。采用X射线衍射(XRD)确定了1200℃煅烧后的晶体粉为纯YAG结构,无杂质相,晶体尺寸约为90nm;该粉体在波长为980nm的半导体激光器激发下发射出中心波长为487nm的蓝色上转换荧光,对应于Tm3+离子的1G4→3H6的跃迁。发光强度和激发功率关系的研究揭示了其为双光子过程,Tm3+的激发态吸收及Tm3+、Yb3+间的交叉驰豫型能量传递和是该上转换发光的主要机制。     

钇或钕掺杂TiO_2纳米纤维的制备及光催化性能研究

采用静电纺丝技术,以Ti(SO4)2、聚乙烯吡咯烷酮(PVP,Mr=1300000)、稀土氧化物和N,N-二甲基甲酰胺(DMF)为原料,成功地制备了TiO2、Y/TiO2和Nd/TiO2纳米纤维.用XRD、FESEM、TEM和TG-DTA等分析手段对样品进行了表征.XRD分析结果表明,当焙烧温度为550℃时得到纯锐钛矿相RE/TiO2(RE=Y,Nd)纳米纤维,900℃时得到纯金红石型RE/TiO2(RE=Y,Nd)纳米纤维,稀土离子显著降低了TiO2的晶格参数.FESEM分析结果表明,RE/TiO2(RE=Y,Nd)纳米纤维直径约为50nm、长度300μm.以罗丹明B和苯酚为目标降解物,研究了三种催化剂的光催化性能.其中,1.5mol%Y/TiO2光催化剂对罗丹明B的降解效率较高,而1.0mol%Nd/TiO2对苯酚具有较好的降解活性.因此,掺杂不同稀土离子的TiO2纳米纤维对不同降解物的降解能力不同.     

铒单掺和铒/镱共掺氟氧玻璃的上转换发光性质研究

研究了室温下掺不同摩尔分数Er3+单掺和Er3+/Yb3+双掺的20GaF3-15InF3-17CdF2-15ZnF2-10SnF2-3P2O5-(20-x-y)PbF2-xErF3-yYbF3(x=0.1~0.4,y=1~4)氟氧玻璃的上转换发光性质。755nm激发下,在Er3+单掺系列玻璃中观察到紫色(410nm)、蓝色(465nm)和绿色(522nm、544nm)上转化发光,随着掺杂Er3+浓度的增大,各荧光强度增幅有变缓的趋势。980nm激发下,由于Yb3+的敏化作用,在Er3+/Yb3+双掺系列玻璃中观察到绿色(548nm、527nm)和红色(661nm)上转换发光,固定Er3+浓度,随着Yb3+浓度的增大,各荧光强度先增大后减小,当Yb3+、Er3+掺杂浓度比为15时发光强度最大。该氟氧玻璃具有比氟化物玻璃更好的抗析晶稳定性,掺稀土离子后在不同波长激发下可观察到明亮的红、绿色上转换荧光,是一种有潜质用于红、绿色上转换发光的材料。     

掺杂钇铋Ce-Zr-Al储氧材料的制备及性能研究

采用共沉淀法制备了掺杂Y3+、Bi3+的CeO2-ZrO2-Al2O3(CZA)储氧材料,并通过XRD、低温N2吸附-脱附、氧脉冲吸附(OSC)及H2-TPR等手段进行了表征.XRD结果表明,600℃和1000℃焙烧后,Y3+、Bi3+的加入没有改变物相结构,所有样品均形成单一立方相萤石结构固溶体.低温N2吸附结果表明,Y3+掺杂的Ce0.6Zr0.3Y0.1O1.95-Al2O3(CZYA)材料,其织构性能及热稳定性都有很大的改善,1000℃老化5h后,比表面积和孔容可分别达80.75m2/g和0.22mL/g.OSC和H2-TPR结果表明,同时掺杂Y3+、Bi3+的Ce0.6Zr0.2Y0.1Bi0.1O1.9-Al2O3(CZYBA)材料,其储氧性能明显增强,经600和1000℃焙烧后分别达到461和242μmol/g;同时掺杂Y3+、Bi3+增强了CZA材料的还原性能,1000℃老化5h后还原峰温度从546℃降低到429℃.     

Sm3+和Gd3+共掺杂TiO2粉体的制备和性能表征

采用溶胶-凝胶法制备了纯TiO2,1%Sm3+或2%Gd3+单掺杂和1%Sm3+/2%Gd3+共掺杂TiO2复合粉体,采用XRD和SEM/EDAX等技术进行表征。以对亚甲基蓝的光催化降解为目标反应,评价了TiO2复合粉体的光催化活性,探讨了Sm3+/Gd3+共掺杂、亚甲基蓝初始浓度和粉体投加量对TiO2粉体光催化活性的影响机制。结果表明,Sm3+/Gd3+共掺杂可以显著提高TiO2粉体的光催化活性;Sm3+/Gd3+共掺杂在TiO2粉体中产生协同作用,抑制了TiO2由锐钛矿相向金红石相转变,使TiO2粒径尺寸减小,增大了TiO2的晶格畸变。当亚甲基蓝初始浓度为4mg/L和粉体投加量为2g/L时,TiO2复合粉体的光催化活性最高,对亚甲基蓝光催化降解率达99.71%;降解亚甲基蓝反应符合Langmuir-Hinshelwood动力学方程。     

Gd~(3+)对(Y,Gd)BO_3:Eu~(3+)发光性质的影响

采用共沉淀法制备了YGB:Eu~(3+)红色荧光粉.XRD研究表明,Gd~(3+)的掺入使其晶胞参数增加,并引起一定程度的晶格畸变.YGB:Eu~(3+)中Eu~(3+)的VUV激发发射主要借助于基质吸收,而CTS亦起一定作用.YGB:Eu~(3+)的基质吸收带与CTS均有一定的红移,强度有一定变化.在UV区存在Gd~(3+)→,Eu~(3+)的能量传递.由于Eu~(3+)5s5p轨道对晶场的屏蔽作用,Gd~(3+)浓度基本不影响发射峰的位置.Gd~(3+)浓度的增加,色纯度有一定的改善.Gd~(3+)的掺入影响了晶体对称性并使晶体中A格位数目增加是主要原因.适度的晶格畸变有利于基质对能量的吸收,使Eu~(3+)辐射效率达到最大,适宜的Gd~(3+)的浓度约为0.3mol.     

Effect of structure, particle size and relative concentration of Eu(3+) and Tb(3+) ions on the luminescence properties of Eu(3+) co-doped Y(2)O(3):Tb nanoparticles

Eu(3+) co-doped Y(2)O(3):Tb nanoparticles were prepared by the combustion method and characterized for their structural and luminescence properties as a function of annealing temperatures and relative concentration of Eu(3+) and Tb(3+) ions. For Y(2)O(3):Eu,Tb nanoparticles annealed at 600 and 1200?°C, variation in the relative intensity of excitation transitions between the (7)F(6) ground state and low spin and high spin 4f(7)5d(1) excited states of Tb(3+) is explained due to the combined effect of distortion around Y(3+)/Tb(3+) in YO(6)/TbO(6) polyhedra and the size of the nanoparticles. Increase in relative intensity of the 285?nm peak (spin-allowed transition denoted as peak B) with respect to the 310?nm peak (spin-forbidden transition denoted as peak A) with decrease of Tb(3+) concentration in the Y(2)O(3):Eu,Tb nanoparticles heated at 1200?°C is explained based on two competing effects, namely energy transfer from Tb(3+) to Eu(3+) ions and quenching among the Tb(3+) ions. Back energy transfer from Tb(3+) to Eu(3+) in these nanoparticles is found to be very poor.     

The properties of upconversion luminescence on YAIO3:Er(3+) nanophosphors with different Er(3+) concentrations

We report the properties of upconversion luminescence on Yttrium aluminum perovoskite (YAIO3) doped with trivalent erbium at concentrations of 1, 2, 3, 5 and 7 mol%. The samples were synthesized by solvo-thermal reaction method and the XRD patterns conforms that the YAP:Er(3+) nanophosphors have orthorhombic phase. Efficient green and red upconversion (UC) emission of YAP:Er(3+) nanophosphors was measured under the excitation of 975 nm continuous wave diode laser, and its dynamics and pump power dependence were investigated. As concentration of Er(3+) ion increased from 1 to 7 mol%, the red UC emission increased more rapidly. It is attributed to the energy transfer (4I(11/2) --> 4I(15/2):4I(13/2) --> 4F(9/2)) and to the cross relaxation (4S(3/2) --> 4I(9/2):4I(15/2) --> 4I(13/2)) between Er(3+) ions. In this case, the green and red emissions were yielding from quadratic to linear. These conclusions obtained are confirmed by theoretical investigations based on steady-state rate equations.     

Gd~(3+)、Sm~(3+)共激活La_2O_2S:Eu~(3+)的发光特性

利用高温固相反应法合成了La2O2S:Eu3+及La2O2S:EC'、Sm3+、Gd3+荧光粉,并对其进行了表征.X射线衍射测试结果表明,合成样品为La2O2S纯物相,激光粒度分析测得荧光粉的平均粒径为18μm.光谱测试表明,Sm3+、Gd3+的掺入能有效增强Eu3+的627nm发射强度,所合成的(La0.945 Gd0.01Sm0.005Eu0.03)2O2S荧光粉是一种具有应用前景的红色光致发光材料.     

Biofunctionalization of CeF(3):Tb(3+) nanoparticles

CeF(3):Tb(3+) nanoparticles (short pillar-like morphology with an average length and width of 11 and 5?nm, respectively) were successfully prepared by a polyol process using diethyleneglycol (DEG) as solvent. After being functionalized with a SiO(2)-NH(2) layer, these CeF(3):Tb(3+) nanoparticles can be conjugated with biotin molecules (activated by thionyl chloride) and further with avidin. The as-formed CeF(3):Tb(3+) nanoparticles, CeF(3):Tb(3+) nanoparticles functionalized with amino groups, biotin conjugated amino-functionalized CeF(3):Tb(3+) nanoparticles and biotinylated CeF(3):Tb(3+) nanoparticles bonded with avidin were characterized by x-ray diffraction (XRD), transmission electron microscopy (TEM), Fourier transform infrared (FT-IR), UV/vis absorption spectra and luminescence spectra, respectively. The biofunctionalization of the CeF(3):Tb(3+) nanoparticles has less effect on their luminescence properties, i.e. they still show strong green emission (from Tb(3+), with (5)D(4)-(7)F(5) at 543?nm as the most prominent group), indicative of the great potential for these CeF(3):Tb(3+) nanoparticles to be used as biological fluorescence probes.     

Emission properties of hydrothermal Yb(3+), Er(3+) and Yb(3+), Tm(3+)-codoped Lu2O3 nanorods: upconversion, cathodoluminescence and assessment of waveguide behavior

Yb(3+) and Ln(3+) (Ln(3+) = Er(3+) or Tm(3+)) codoped Lu(2)O(3) nanorods with cubic Ia3 symmetry have been prepared by low temperature hydrothermal procedures, and their luminescence properties and waveguide behavior analyzed by means of scanning near-field optical microscopy (SNOM). Room temperature upconversion (UC) under excitation at 980 nm and cathodoluminescence (CL) spectra were studied as a function of the Yb(+) concentration in the prepared nanorods. UC spectra revealed the strong development of Er(3+) (4)F(9/2) → (4)I(15/2) (red) and Tm(3+) (1)G(4) → (3)H(6) (blue) bands, which became the pre-eminent and even unique emissions for corresponding nanorods with the higher Yb(3+) concentration. Favored by the presence of large phonons in current nanorods, UC mechanisms that privilege the population of (4)F(9/2) and (1)G(4) emitting levels through phonon-assisted energy transfer and non-radiative relaxations account for these observed UC luminescence features. CL spectra show much more moderate development of the intensity ratio between the Er(3+) (4)F(9/2) → (4)I(15/2) (red) and (2)H(11/2), (4)S(3/2) → (4)I(15/2) (green) emissions with the increase in the Yb(3+) content, while for Yb(3+), Tm(3+)-codoped Lu(2)O(3) nanorods the dominant CL emission is Tm(3+) (1)D(2) → (3)F(4) (deep-blue). Uniform light emission along Yb(3+), Er(3+)-codoped Lu(2)O(3) rods has been observed by using SNOM photoluminescence images; however, the rods seem to be too thin for propagation of light.     

Optical characterization of Nd (3+):AgBr

The luminescence of silver bromide crystals, doped with neodymium, was investigated over the visible and near-infrared spectral ranges. The emission, excitation, and absorption spectra were measured over a broad temperature range. The absolute luminescence quantum yield was estimated by comparing the luminescence with that of a neodymium-doped phosphate glass, for which the manufacturer gives a value of 0.4. The Judd-Ofelt analysis was applied to both materials, and transition rates, branching ratios, and quantum efficiencies were calculated for all the observed bands. Good agreement was obtained between theory and experiment.     

Luminescence Characteristics and Energy Transfer Machanismof LaOBr:Tb~(3+) (Dy~(3+))

The rare earth luminescence materials LaOBrfTb3+(Dy3+) were synthesized at high temperature,and the structure and luminescence characteristics were studied. The co-doping Dy3+ may make the energy of 5D3 of Tb3+ transfer to 5D4 level, which makes the emission of 5D4-7FJ (J=0,1... 6), specially of 5D4-7F5, enhance obviously, and the total brightness is increased by about 40% in comparison with the samples without Dy3+ cations, as a result of the energy transfer of dipole-dipole interaction.     

Hydrothermal synthesis and optical properties of Eu(3+)-doped CaSnO3 nanocrystals

In this paper, CaSnO3:Eu3+ nanocrystals were prepared by hydrothermal synthesis method. The influence of different molar ratio of Ca:Sn on structure of CaSnO3:Eu3+ was investigated by using X-ray powder diffraction (XRD). Well-crystallized and phase-pure CaSnO3:Eu3+ particles of approximately 90 nm in size can be readily obtained at 900 degrees C. Furthermore, photoluminescence characterization of the Eu(3+)-doped CaSnO3 nanocrystals was performed and discussed. The emission peak situated at 618 nm showing prominent and bright red light is due to the 5D0-7F2 electric dipole transition. The excellent luminescence properties make it possible as a good candidate for PDP application.     

不同煅烧温度及气氛制备Gd~(3+)-C~(4+)掺杂TiO_2的光催化活性

为了研究Gd3+、C4+离子掺杂Ti O2粉体的光催化活性,选取不同Gd3+、C4+加入量、煅烧温度、气氛等因素,采用溶胶-凝胶法制备Gd3+-C4+掺杂Ti O2复合粉体;通过X射线衍射、显微图像观察、表面及孔隙度分析等手段对复合粉体的物相、形貌及光催化活性进行表征。结果表明:Gd3+-C4+掺杂Ti O2复合粉体在N2气氛中经550℃煅烧2 h后,粉体分散较好,Ti O2仍为锐钛矿结构;当Gd3+与C4+的物质的量比为0.06时,复合粉体在太阳光下照射3 h后,对罗丹明B的降解率可达90%。     

ZrO2陶瓷中Zr^4＋和Y^3＋的近邻结构与相稳定性

采用ＥＸＡＦＳ方法研究了经中温等温和低温ＬＮ２处理的２ｍｏｌ％Ｙ２Ｏ３－ＺｒＯ２陶瓷中Ｚｒ＾４＋和Ｙ＾３＋离子的近邻结构。结果表明,与中温等温试样相比,ＬＮ２处理的试样中Ｚｒ－Ｏ层和Ｚｒ－Ｚｒ（Ｙ）层的配位数显著减少,平均键长明显减小,Ｙ－Ｏ层配位数减少,Ｙ－Ｚｒ（Ｙ）层平均键长增长;各配位层畸变程度均增大。分析认为,该试样Ｚｒ－Ｏ配位层中较多的氧空位主要来源于从高温快速冷却时所保留下来的Ｓｃｈｏ     

Passively Q-switched Tm(3+)-doped silica fiber lasers

By splicing on a length of Ho(3+)-doped silica fiber onto a diode-pumped double-clad Tm(3+)-doped silica fiber, stable passive Q switching of the Tm(3+)-doped silica fiber laser is demonstrated. The formation of Q-switched pulses was found to depend on both the length and the position of the Ho(3+)-doped silica fiber that was inserted into the fiber laser cavity. For stable Q-switched pulse generation, Ho(3+)-doped silica fiber lengths shorter than twice the absorption depth must be used. For long Ho(3+)-doped silica fiber lengths, randomly generated pulses are observed at operating wavelengths longer than 2090 nm, which are attributed to intracavity pumping of the Ho(3+)-doped silica fiber.     

Fabrication of novel luminor Y(2)O(3):Eu(3+)@SiO(2)@YVO(4):Eu(3+) with core/shell heteronanostructure

A novel polychromic phosphor with core-shell heteronanostructure has been prepared to improve the chromatic index of phosphors. As for the first example, Y(2)O(3):Eu(3+)@SiO(2)@YVO(4):Eu(3+), its synthetic route, structure and optical properties are presented in this paper. X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM), high resolution transmission electron microscopy (HR-TEM), energy-dispersive x-ray spectra (EDS) and photoluminescence (PL) were all employed to characterize the composite core-shell phosphors. The XRD, FE-SEM and HR-TEM results indicate that the SiO(2) and YVO(4):Eu(3+) layers have been successfully coated on Y(2)O(3):Eu(3+) nanoparticles and SiO(2) layer, respectively: these layers were further verified by the EDS. The PL showed that the red-emitting phosphor Y(2)O(3):Eu(3+)@SiO(2)@YVO(4):Eu(3+) possessed the independent luminescent properties of both the core Y(2)O(3):Eu(3+) and the shell YVO(4):Eu(3+). The emissions were dominated by [Formula: see text] or [Formula: see text] transitions of Eu(3+) when excited with different wavelengths. Since this broad-band response to excitation in the range of 225-340?nm gave more red/dark red emissions found at 612, 616 and 620?nm, the novel phosphor Y(2)O(3):Eu(3+)@SiO(2)@YVO(4):Eu(3+) could have potential biological labeling applications with wide flexibility.     

Er~(3+)/Yb~(3+)/Tb~(3+)共掺氟氧锗酸盐玻璃上转化发光性质及机理研究(英文)

在980nm激发下,研究了Er3+、Yb3+和Tb3+单掺或共掺氟氧锗酸盐玻璃的上转换发光性质和机理.室温下,观察到了强的绿色和红色上转换发光,其发光中心位于524、546和658nm处,分别对应于Tb3+离子的5D4→7FJ(J=5和0)和Er3+离子的(2H11/2、4S3/2和4F9/2)→4I15/2跃迁.研究了TbF3、YbF3掺杂浓度以及激光功率对上转换发光强度的影响,讨论了Er3+、Yb3+和Tb3+之间的能量传递和上转换机理.