Er~(3+)/Yb~(3+)共掺四种玻璃中上转换发光效率的比较及研究

计算了在Er3+/Yb3+共掺的硅酸盐、锗酸盐、磷酸盐和氟化物这四种玻璃基质中施主离子归一化荧光线形函数与受主离子归一化吸收线形函数的重叠积分,交叉弛豫几率.通过求解能级跃迁速率方程,得出4S3/2能级的相对布居数.定义了上转换发光效率可以用自发辐射跃迁几率A61和4S3/2能级的相对布居数之积来表征.分析了由于氟化物中4S3/2能级的无辐射跃迁几率较小而自发辐射跃迁几率较大,因此4S3/2能级有较大的相对布居数,在四种Er3+/Yb3+共掺的玻璃中,氟化物具有较好的上转换发光效率.     

颜色可调Y(PO3)3:Tb3+,Yb3+上转换发光材料的共沉淀制备及性能

采用共沉淀法制备Tb3+,Yb3+共掺杂Y(PO3)3上转换发光材料,通过X射线粉末衍射仪(XRD)、扫描电镜(SEM)、傅里叶红外光谱(FT-IR)和上转换荧光光谱仪(UPL)对制备产物的结构和性能进行表征分析.结果表明,所制备样品属于单斜晶系空间群为P21/c的Tb3+和Yb3+共掺杂Y(PO3)3晶体.在近红外光的激发下,所制备Y(PO3)3:x Tb3+,20％(摩尔分数,下同)Yb3+样品发射出Tb3+特征的蓝绿色光.Tb3+掺杂量直接影响着制备产物的上转换发光性能,当Tb3+掺杂量为2％ ～10％时,Tb3+的5 D4→7 F6发射峰分裂为481 nm和491 nm两个发射峰;当掺杂量为5％～20％时,位于547 nm处绿光发射为最强发射峰;当Tb3+掺杂量高于20％时观察到浓度猝灭现象.Tb3+/Yb3+的掺杂量比例和近红外光激发功率密度对所制备样品的上转换发光性能也有明显影响.适当调节样品中Tb3+/Yb3+掺杂比例可实现对制备的Y(PO3)3:x Tb3+,20％Yb3+样品的上转换发射蓝绿光颜色的调控.对Y(PO3)3:Tb3+,Yb3+样品的上转换发光机理进行探索,其中属于Tb3+特征的5 D3→7 FJ(J=6,5,4)和5 D4→7 FJ(J=6,5,4,3)跃迁带发射分别属于三光子吸收和双光子吸收机制.     

PEG修饰YF_3微米晶的溶剂热合成及Y_(1.2)F_3:Yb_(0.18)~(3+)/Er_(0.01)~(3+)上转换荧光性质

采用溶剂热方法,乙醇和乙二醇的混合溶剂中,150℃条件下,反应12h,成功制备了YF3:Yb3+/Er3+晶体,和PEG-6000修饰的YF3:Yb3+/Er3+晶体。通过X射线粉末衍射,扫描电镜(SEM),红外光谱(IR)和荧光分光光度计对样品的组成、结构和荧光性质进行了表征和分析。结论为:YF3:Yb3+/Er3+晶体与YF3标准卡PDF#74-0911相符,而PEG-6000修饰的YF3:Yb3+/Er3+晶体的标准卡为PDF#32-1431,说明PEG的修饰导致晶体结构的变化。室温下,以980nm为激发光源,YF3:Yb3+/Er3+晶体和PEG修饰的YF3:Yb3+/Er3+晶体的荧光发射峰位置均为551nm、666nm和832nm,其分别对应于Er3+离子的4S3/2→4I15/2,4F9/2→4I15/2和4S3/2→4I13/2跃迁。但荧光强度不同。讨论了表面活性剂聚乙二醇的加入对YF3:Yb3+/Er3+晶体形貌,尺寸及荧光性质的影响,并对Yb3+/Er3+上转换发光机理进行了讨论。     

P2O3-B2O3-Al2O3-SrO-BaO玻璃中Yb3+非辐射能量转移下Er3+离子的增强发射

本文研究了共掺Er3 +/Yb3 +P2 O3 -B2 O3 -Al2 O3 -SrO -BaO玻璃的能量转移过程。实验中制备了高掺杂Yb3 +离子的双掺Er3 +/Yb3 +的磷酸盐玻璃样品。在Er3 +/Yb3 +掺杂比率 >1 :1 8(mol% )时 ,观测到了基于Yb3 +离子至Er3 +离子能量转移下Er3 +( 4 I13 / 2 →4I15 / 2 )的增强发射和Yb3 +( 2 F7/ 2 →2 F5 / 2 )发射的减弱 ,当Yb3 +离子掺杂浓度超过 2 .1× 1 0 2 1ions/cm3 时 (Er3 +/Yb3 +≤ 1 :1 8,mol% ) ,由于Yb3 +离子的自淬灭效应 ,Er3 +离子的发射强度降低。实验中得到了Yb3 +离子的最佳掺杂浓度为1 .74× 1 0 2 1ions/cm3     

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。     

稀土掺杂TiO2在1064nm激光激发下的上转换发光

为研究TiO2材料的上转换发光特性,采用溶胶-凝胶与共沉淀法制备了La3+、Yb3+和Er3+稀土离子掺杂的TiO2粉末.利用SEM和XRD表征发光材料的结构,探讨了试样在1064nm激发光源常温激发作用下,稀土氧化物的掺杂比例、煅烧温度对上转换发光特性的影响.实验表明,1064nm激光常温激发TiO2基掺杂稀土La2O3、Yb2O3、Er2O3的最佳比例为39∶ 10∶1,经1300℃煅烧可制备出明亮绿色发光的上转换材料.     

核壳结构NaYF_4:Yb~(3+)、Er~(3+)/SiO_2颗粒的制备及其光谱性能

以正硅酸乙酯为原料,采用水解法,对100 nm亲水及20 nm亲油的NaYF4:Yb3+、Er3+上转换发光纳米颗粒进行了表面修饰,制备出了NaYF4:Yb3+、Er3+/SiO2核壳结构.研究了反应时间、反应前驱体浓度等工艺条件对包覆效果的影响.结果表明,经过二氧化硅包覆后的亲水及亲油大、小颗粒都可以均匀地分散在亲水溶剂中.在室温下,分别对SiO2壳层包覆前后的NaYF4:Yb3+、Er3+纳米颗粒的上转换发光光谱进行对比研究,发现两种粒子都能在980 nm激光激发下,产生550 nm的绿光及670 nm的红光,且包覆后纳米颗粒的发光位置及整体发光强度与包覆前相比没有受到影响.     

CeO2∶Er3+纳米晶的合成及上转换发光特性研究

采用燃烧法制备得到CeO2∶Er3+纳米晶粉末.用X射线衍射仪(XRD)、高分辨透射电子显微镜(HRTEM)和荧光分光光度计等对CeO2∶Er3+纳米晶的结构、形貌和上转换发光特性进行了研究.结果表明:所得到的纳米晶粒度均匀、结晶完好,属于立方萤石结构.上转换发光光谱的研究表明:在980nm红外光激发下,可以发现上转换荧光,分别来自于Er3+离子的2H11/2,4S3/2→4 I15/2和4 F9/2→4I15/2跃迁.     

Er~(3+)掺杂透明微晶玻璃光谱性质的研究

通过高温熔融法和热处理制备了含有-γBi2WO6纳米晶的Er3+掺杂透明硼铋酸盐微晶玻璃.根据X射线粉末衍射结果和Scherrer公式计算得到-γBi2WO6晶粒大小约为15 nm.由于部分Er3+离子取代Bi3+进入-γBi2WO6纳米晶相中,使得Er3+离子在1.5μm的有效发射带宽由78 nm增加到85 nm,同时Er3+离子在4I13/2能级的荧光寿命由0.67 ms增加到1.43 ms.此外,与原始玻璃相比,在Er3+掺杂硼铋酸盐微晶玻璃中观察到强烈的绿光上转换发光,其上转换发光机制可以归为双光子过程.     

Yb~(3+)/Tm~(3+)共掺杂BST铁电厚膜的制备及其上转换发光

利用丝网印刷工艺制备出稀土Yb3+/Tm3+共掺杂的Ba0.8Sr0.2TiO3铁电陶瓷厚膜,利用XRD、SEM、EDS、Raman和荧光光谱仪研究了稀土掺杂对厚膜微结构和发光性能的影响。实验发现,在低掺杂量时Yb3+、Tm3+离子在BST晶格中首先替代B位离子,高掺杂量时则同时占据A位和B位离子。掺杂后的厚膜仍表现为典型的铁电四方相结构。在800nm近红外激光激发下,共掺杂的BST厚膜中的Tm3+离子通过Yb3+离子的敏化作用在468与533nm处实现了间接上转换蓝色与绿色荧光输出,分别对应于Tm3+离子的1 G4→3 H6跃迁和1 D2→3F4跃迁。468nm蓝色荧光强度随着Yb3+、Tm3+离子比的增加先增强后减弱,在Yb3+、Tm3+离子共掺比为2∶1达到最大,并对上转换发光的机理进行了分析。     

Photoluminescence and doping mechanism of theranostic Eu3+/Fe3+ dual-doped hydroxyapatite nanoparticles

Theranostic nanoparticles currently have been regarded as an emerging concept of ‘personalized medicine’ with diagnostic and therapeutic dual-functions. Eu³⁺ doped hydroxyapatite (HAp) has been regarded as a promising fluorescent probe for in vivo imaging applications. Additionally, substitution of Ca²⁺ with Fe³⁺ in HAp crystal may endow the capability of producing heat upon exposure to a magnetic field. Here we report a preliminary study of doping mechanism and photoluminescence of Eu³⁺ and Fe³⁺ doped HAp nanoparticles (Eu/Fe:HAp). HAp with varied concentration of Eu³⁺ and Fe³⁺ doping are presented as Eu(10 mol%):HAp, Eu(7 mol%)-Fe(3 mol%):HAp, Eu(5 mol%)-Fe(5 mol%):HAp, Eu(3 mol%)-Fe(7 mol%):HAp, and Fe(10 mol%):HAp in the study. The results showed that the HAp particles, in nano-size with rod-like morphology, were successfully doped with Eu³⁺ and Fe³⁺, and the particles can be well suspended in cell culture medium. Photoluminescence analysis revealed that particles have prominent emissions at 536 nm, 590 nm, 615 nm, 650 nm and 695 nm upon excitation at a wavelength of 397 nm. Moreover, these Eu/Fe:HAp nanoparticles belonged to B-type carbonated HAp, which has been considered an effective biodegradable and biocompatible drug/gene carrier in biological applications.     

YAG:Ce3+, Gd3+ nano-phosphor for white light emitting diodes

YAG:Ce³⁺, Gd³⁺ nano-phosphors were synthesised by the glycothermal method. The X-ray diffraction measurements showed that the samples can be well-crystallised at 600°C. The transition electron microscope showed that the particles have sizes mostly in the range between 35 and 100?nm. The YAG:Ce nano-phosphor had a wide emission band ranging from blue to yellow with a peak at 532?nm, due to the transition from the lowest 5d band to ²F_7/2, ²F_5/2 states of the Ce³⁺ ion. Red-shift of emission peak wavelength from 532 to 568?nm was achieved doping Gd³⁺ ions into the YAG:Ce³⁺ to substitute some Y³⁺ ions. White light emitting diodes (LEDs) were obtained by combining blue LED chip (InGaN-based 460?nm emitting) with (Y_{2.94? x} Ce_0.06Gd _x )Al₅O₁₂ phosphor. As x has the value of 0.8, an intense white LED with good colour rendering of 86 was obtained.     

Kinetic study of Cu(II) adsorption on nanosized BaTiO(3) and SrTiO(3) photocatalysts

In this study, nanoparticles with perovskite structure (nano-SrTiO(3) and nano-BaTiO(3)) were synthesized via a co-precipitation method, and their photocatalytic and adsorption characteristics were investigated. Both of them exhibited some photocatalytic activity and possessed a high adsorption capacity for copper ions. Further, the pseudo-first-order model was found to be more suitable to fit the experimental data. Moreover, it suggested that the Langmuir model was more adequate in simulating the adsorption isotherm. The maximum adsorption capacity was 370.4 mg/g and 200.0mg/g for nano-SrTiO(3) and nano-BaTiO(3), respectively. The negative apparent free energy confirmed that the Cu(2+) adsorption onto the nano-photocatalysts was a spontaneous process. The underlying mechanism of adsorption of Cu(II) onto nano-perovskites could be due to the ion exchange and surface complexation. From the results, SrTiO(3) and BaTiO(3) nanoparticles may be an effective material for Cu(2+) removal and, together with its photocatalytic activity, may be suitable for environmental remediation applications.     

Ho~(3+)掺杂Ge-Ga-S-CsI玻璃中红外发光性能研究

采用熔融冷却法制备了系列不同Ho3+离子掺杂浓度的Ge-Ga-S-CsI玻璃样品,测试了样品的折射率、吸收光谱以及中红外荧光光谱和Ho3+离子5I6能级荧光寿命.应用Judd-Ofelt理论计算了Ho3+离子在该基质玻璃中强度参数Ωi(i=2,4,6)、能级跃迁振子强度fcal、自发跃迁几率Arad等光谱参数.计算了Ho3+:5I5→5I6(3.86μm)和5I6→5I7(2.81μm)跃迁的多声子驰豫速率.讨论了中红外荧光特性与Ho3+离子掺杂浓度之间的关系.结果表明,在900nm激光泵浦下观察到了2.81和3.86μm两处中红外荧光,分别对应于Ho3+:5I6→5I7和5I5→5I6跃迁,当Ho3+离子掺杂浓度从0.5wt%增加到1.0wt%时,两处中红外荧光强度都随相应增加,计算的Ho3+:5I5→5I6和5I6→5I7跃迁多声子驰豫速率分别为29s-1和34s-1.     

White light emission of Dy3+-doped and Dy3+:Yb3+-codoped oxyfluoride glass ceramics under 388-nm excitation

Dy³⁺-doped and Dy³⁺:Yb³⁺-codoped oxyfluoride glass ceramics have been prepared by high-temperature solid phase sintering method. The micrographs of scanning electron microscope show that a lot of nanorods are formed on the surface of Dy³⁺:Yb³⁺-codoped sample. The excitation spectra and emission spectra are measured, respectively, and intense photoluminescence peaks at 482 and 575 nm corresponding to the transitions of Dy³⁺ ions are found in single-doped samples under 388-nm excitation. For Dy³⁺:Yb³⁺-codoped oxyfluoride glass ceramics, the intensities at blue and green bands become weaker whereas the intensity at 695 nm gets stronger. The indirect sensitization is detailedly discussed and Commission Internationale de l′E-clairage chromaticity coordinates exhibit that two kinds of oxyfluoride glass ceramics are available candidates for the solid-state white light emission.     

Novel blue-emitting phosphor NaMg4(PO4)3:Eu, Ce with energy transfer

A blue-emitting phosphor of NaMg₄(PO₄)₃:Eu²⁺, Ce³⁺ was prepared by a combustion-assisted synthesis method. The phase formation was confirmed by X-ray powder diffraction measurement. Photoluminescence excitation spectrum measurements show that the phosphor can be excited by near UV light from 230 to 400 nm and presents a dominant luminescence band centered at 424 nm due to the 4f⁶5d¹ → 4f⁷ transition of Eu²⁺ ions at room temperature. Effective energy transfer occurs in Ce³⁺/Eu²⁺ co-doped NaMg₄(PO₄)₃ due to large spectral overlap between the emission of Ce³⁺ and excitation of Eu²⁺. Co-doping of Ce³⁺ enhances the emission intensity of Eu²⁺ greatly by transferring its excitation energy to Eu²⁺, and Ce³⁺ plays a role as a sensitizer. Ce³⁺-Eu²⁺ co-doped NaMg₄(PO₄)₃ powders can possibly be applied as blue phosphors in the fields of lighting and display.     

Fast d-f emission in Ce, Pr and Nd activated RbCl

In the search for new scintillator materials, Ce³⁺ doped chlorides are a promising class of materials, combining a high efficiency and fast response time. Even shorter response times may be achieved by replacing Ce³⁺ by Pr³⁺ or Nd³⁺ as the lifetime of the d-f emission is substantially shorter for these ions. Here we report on the luminescence properties of Ce³⁺, Pr³⁺ and Nd³⁺ in RbCl and investigate the potential as a scintillator material. Under UV excitation Ce³⁺ shows d-f emission between 325 and 425 nm. The emission originates from multiple (differently charge compensated) Ce³⁺ sites. The luminescence lifetime varies with wavelength and is ∼40 ns for the longer wavelength emission. For RbCl:Pr³⁺ three d-f emission band are observed between 250 and 350 nm which can be assigned to transitions from the lowest energy fd state to different ³H_J (J = 4-6) states within the 4f² configuration of Pr³⁺. The decay time is ∼17 ns. For the Nd³⁺ activated sample a weak emission band around 220 nm is observed only at 8 K which may be due to d-f emission. The very short lifetime (4 ns) is faster than the radiative lifetime, indicating that the d-f emission is quenched by relaxation to lower lying 4f³ states or by the process of photoionization. Under VUV excitation at wavelengths below 175 nm (the bandgap of RbCl) the d-f emission is very weak for Ce³⁺, Pr³⁺ and Nd³⁺ doped RbCl and the emission spectra are dominated by defect related emission. This indicates that energy transfer from the host lattice to the fd states is inefficient which prevents application as a scintillator material.     

Significant reduction of upconversion emission in CaTiO3: Yb, Er inverse opals

Inverse opal photonic crystals of Yb³⁺, Er³⁺ co-doped CaTiO₃ (CaTiO₃: Yb, Er) were prepared using self-assembled polystyrene templates combined with the infiltration of sol-gel precursor. The influence of the photonic band gap on upconversion emission of Er³⁺ has been investigated in the CaTiO₃: Yb, Er inverse opals. Significant reduction of the upconversion emission was detected if the photonic band-gap overlaps with the Er³⁺ ions emission band.     

A red-emitting heavy doped phosphor Li6Y(BO3)3:Eu for white light-emitting diodes

A series of Eu³⁺ activated Li₆Y_1−xEu_x(BO₃)₃ (0.05 ? x ? 1) phosphors were synthesized by solid-state reaction method. The structures and photoluminescent properties of the phosphors were investigated at room temperature. The results of XRD patterns indicate that these phosphors are isotypic to the monoclinic Li₆Gd(BO₃)₃. The excitation spectra indicate that these phosphors can be effectively excited by near UV (370-410 nm) light. The red emission from transition ⁵D₀→⁷F₂ is dominant. The emission spectra exhibit strong red performance (CIE chromaticity coordinates: x = 0.65, y = 0.35), which is due to the ⁵D₀−⁷F_J transitions of Eu³⁺ ions. The relationship between the structure and the photoluminescent properties of the phosphors was studied. The concentration quenching occurs at x ≈ 0.85 under near UV excitation. Li₆Y(BO₃)₃:Eu³⁺ has potential application as a phosphor for white light-emitting diodes.     

Photoluminescence properties of Y2O3:Tb and YBO3:Tb green phosphors synthesized by hydrothermal method

In this work, two Tb³⁺ activated green phosphors: Y₂O₃:Tb³⁺ and YBO₃:Tb³⁺ were prepared by hydrothermal method. Photoluminescence properties of both phosphors were studied in details. Both phosphors exhibit similar luminescent characteristics symbolized by the dominant green emission at 545 nm. Concentration quenching occurs at the Tb³⁺ concentration of 1.60 atomic% and 2.57 atomic% for Y₂O₃:Tb³⁺ and YBO₃:Tb³⁺, respectively. Luminescence decay properties were characterized to better understand the mechanism of concentration quenching. Based on the calculation, the concentration quenching in both phosphors was caused by the dipole–dipole interaction between Tb³⁺ ions.