Er^3＋/Tm^3＋/Yb^3＋ tridoped oxyfluoride glass ceramics with efficient upconversion white-light emission

A novel Tm^3＋/Yb^3＋ triply-doped glass ceramics containing BaF2 nano-crystals are successfully prepared. Fluoride nanocrystals BaF2 are successfully precipitated in glass matrix, which is affirmed by the X-ray diffraction results. The intense blue （476 nm）, green （543 nm）, and red （656 nm） emissions of the glass ceramics are simultaneously observed at room temperature under 980-am excitation, and the emission luminescence intensity increases significantly compared with the precursor glass, which is attributed to the low phonon energy of fluoride nanocrystals when rare-earth ions are incorporated into the precipitated BaF2 nanocrystals. Under 980-nm excitation at 400 mW, the international commission on illumination （CIE） chromaticity coordinate （X = 0.278, Y = 0.358） of the tridoped oxyfluoride glass ceramics＇ upconversion emissions is close to the standard white-light illumination （X = 0.333, Y= 0.333）. The results indicate that Tm^3＋/Yb^3＋ triply doped glass ceramics can act as suitable materials for potential three-dimensional displays applications.     

Red Up-Conversion Luminescence Process in Oxyfluoride Glass Ceramics Doped with Er^3＋／Yb^3＋

The phonon-assisted quantum cutting (PQC) model is presumed to clarify the red up-conversion luminescence process in Er^3 /yb^3 co-doped glass ceramics by the excitation and emission spectra. The red up-conversion luminescence of Er^3 ions mainly comes from three-photon absorption by the PQC process when the rare earth ions are doped in the g/ass ceramics and excited by 98Ohm pumped-laser. Er^3 ions absorb three-photons and relax to the ^4G11/2 state and then emit red up-conversion luminescence by the PQC process. The factor coefficient for the relation of pump-laser power and up-conversion intensity (P-I) is found by the analysis of excitation spectra of the red luminescence, which plays a major role to understand the true red up-conversion luminescence process. The new P-I relation is explained by the model of PQC.     

Research on upconversion codoped oxyfluoride luminescence in new Er^3＋/Yb^3＋ borosilicate glass ceramics

The upconversion luminescence of Er^3＋/Yb^3＋ ions is researched in a novel transparent oxyfluoride borosil- icate glass and glass ceramics under 980-nm excitation. Fluoride nanocrystals Ba2YF7 are successfully precipitated in glass matrix, which is affirmed by the X-ray diffraction results. Compared with the parent glasses, significant enhancement of upconversion luminescence is observed in the Er^3＋/Yb^3＋ codoped transparent glass-ceramics, which may be due to the variation of coordination environment around Er^3＋ and Yb^3＋ ions after crystallization. The possible upconversion mechanism is also discussed.     

White light generation of glass ceramics containing Ba_2LaF_7：Eu~（2＋）,Tb~（3＋） and Sm~（3＋） nanocrystals

The Eu 2＋ /Tb 3＋ /Sm 3＋ co-doped oxyfluoride glass ceramics containing Ba2LaF7 nanocrystals are prepared in the reducing atmosphere.The X-ray difiraction results show that Eu 2＋ ,Tb 3＋ and Sm 3＋ ions are enriched into the precipitated Ba2LaF7 nanophase after the annealing process.It deduces efficient energy transfers from Eu 2＋ to Tb 3＋ and Sm 3＋ and intenses warm white luminescence of the glass ceramics. Comparing with the glass,the luminescence quantum yield of the glass ceramics is also enlarged by about 3 times.This demonstrates the potential white light-emitting diode application of the glass ceramics produced in this letter.     

Enhancement of up-conversion Yb3＋/Tm3＋/Er3＋ tri-doped tellurite glass luminescence properties in transparent oxyfluoride ceramics

Optically transparent Er3＋/Tm3＋/Yb3＋ tri-doped oxyfluoride tellurite based nano-crystallized glass ceramics with the batching composition of 73TeO2-15ZnO-7ZnF2-3YF3-1.5YbF3-0.3ErF3-0.2TmF3 （mol%） is prepared by a conventional melting quenching and the subsequent heat treatment processes. The sizes of grown nano-crystals in glass matrix appear to be smaller than 100 nm from the scanning electron mi- croscope measurement. Visible up-conversion luminescence of the as melted glass and glass ceramics is investigated. The three-color up-conversion luminescence intensities by 980-nm pumping are increased significantly due to the heat treatment, and the blue intensity increases with a higher magnitude than other wavelengths after heat treatment.     

Upconversion Luminescence of Er3+ Ions in Transparent Germanate Glass Ceramics Containing CaF2 Nanocrystals

The visible upconversion and near-infrared luminescence of Er3＋ ions in germanate glass ceramics containing GaF2 nanocrystals are investigated. The nanocrystals are characterized by x-ray diffraction （XRD） and transmission electron microscopy, showing their mean sizes less than 20hm. High transmittance of the glass ceramics is displayed by absorption spectra. The upconversion luminescence intensity in the glass ceramics increases significantly with increasing temperature. Both the shifts of the XRD peaks and the Stark-split shown in the luminescence spectra indicate the entrance of the Er3＋ ions into the CaF2 nanocrystals, which is confirmed by a Judd-Ofelt analysis. Possible mechanisms of the upconversion luminescence are analyzed.     

Upconversion properties of Er^3＋/Yb^3＋ co-doped TeO2-Nb2O5-Li2O glasses

The Er^3＋/Yb^3＋ co-doped TeO2-Nb2O5-Li2O glass is prepared by conventional melting method, and its upconversion spectra are measured. The intense green upconversion luminescence upon excitation with a 976 nm laser diode is observed with the naked eyes. The dependence of luminescence intensity on the ratio of Yb^3＋/Er^3＋ is discussed in detail, and the relationship between the ratio of green luminescence intensity to red luminescence intensity and the ratio of Yb^3＋/Er^3＋ is also studied, The luminescence intensity increases with the ratio of Yb^3＋/Er^3＋ increasing. The ratio of Yb^3＋/Er^3＋ plays a more important role than the concentration of Er^3＋ in determining the upconversion luminescence intensity. The ratio of green luminescence intensity to red luminescence intensity reaches a maximum when ratio of Yb^3＋/Er^3＋ is 3. Thus the glass could be one of the potential candidates for LD pumping solid-state lasers.     

Transparent Ni^2＋-Doped MgO-Al2O3-SiO2 Glass Ceramics with Broadband Infrared Luminescence

We report on transparent Ni^2＋-doped MgO-Al2O3-SiO2 glass ceramics with broadband infrared luminescence. Ni^2＋-doped MgO-Al2O3-SiO2 glass is prepared by using the conventional method. After heat treatment at high temperature, MgAl2O4 crystallites are precipitated, and their average size is about 4.3 nm. No luminescence is detected in the as-prepared glass sample, while broadband infrared luminescence centred at around 1315 nm with full width at half maximum （FWHM） of about 300 nm is observed from the glass ceramics. The observed infrared emission could be attributed to the ^3T2g（^3F）→^3A2g（^3F） transition of octahedral Ni^2＋ ions in the MgAl2O4 crystallites of the transparent glass ceramics. The product of the fluorescence lifetime and the stimulated emission cross section is about 1.6×10^-24 s cm^2.     

Improved Fluorescence from Tm^3＋/Er^3＋/Ce^3＋ Triply Doped Bismuth-Silicate Glasses for S＋C-bands Amplifiers

Fluorescence of Tm^3＋/Er^3＋ codoped bismuth-silica （BS） glasses and the sensitization of Ce^3＋ are investigated, It shows that Ce^3＋ codoping with Tm^3＋/Er^3＋ in BS glasses results in a quenching of Tm^3＋ ion emission from ^3F4 to the ^3H6 level. Consequently, the 1.47μm emission occurs after the population inversion between the ^3H4 and ^3F4 levels. Furthermore, the codoped glasses show the broad emission spectra over the whole S and C bands with full-width at half-maximum （FWHM） up to about 119nm, as it combines 1.55μm emission band of Er^3＋ with 1.47μm emission band of Tm^3＋ under 800hm excitation.     

Nd^3＋, Yb^3＋ and Ho^3＋ Codoped Oxyfluoride Glass Ceramics with High Efficient Green Upconversion Luminescence

New oxyfluoride g/asses and glass ceramic codoped with Nd3 , Yb3 and Ho3 were prepared. The x-raydiffraction analysis revealed that the heat treatments of the oxyfluoride g/asses could cause the precipitationof (Nd^3 , Yb^3 , Ho^3 )-doped fluorite-type crystals. Very strong green up-conversion luminescence due to theHo3 : (^5F4, ^5S2)→ ^5I8 transition under 800-nm excitation was observed in these transparent glass ceramics.The intensity of the green up-conversion luminescence in a 1-mo1% YbF3-containing glass ceramic was found tobe about 120 times stronger than that in the precursor oxyfluoride glass. The reason for the highly efficient Ho^3 up-conversion luminescence in the oxyfluoride g/ass ceramics is discussed.     

二价碱土金属氟化物对Er3+/Tm3+/Yb3+共掺氟氧锗酸盐玻璃热稳定性和光谱特性影响的研究

制备了分别含有MgF2,CaF2,SrF2或BaF2的Er3+/Tm3+/Yb3+共掺氟氧锗酸盐玻璃试样和包含BaF2纳米晶的玻璃陶瓷试样,所制备试样均具有良好的透光性。对试样的热稳定性和上转换发光特性进行了研究。通过分析试样的吸收光谱发现,随着所含二价阳离子原子量的增大,试样的紫外吸收截止波长明显向短波方向移动。结果显示:通过改变所含二价碱土金属离子的种类能够对激发光的颜色进行调节,特别值得关注的是Mg2+的影响;结果证实:通过对包含二价碱土金属的玻璃进行微晶化处理或者增加二价碱土金属的含量均能提高上转换发光的强度。     

Dy3+单掺和Er3+,Yb3+共掺氧氟微晶玻璃的发光性能

采用高温熔融法和热处理工艺制作了含有GdF3纳米晶的氧氟微晶玻璃。在386 nm激发下,Dy3+掺杂氧氟微晶玻璃的发光强度明显增强,且蓝光对黄光的发光强度比逐渐增大,表明Dy3+已进入到GdF3纳米晶中。在980 nm激光器泵浦下,Er3+,Yb3+共掺氧氟微晶玻璃的上转换发光随着热处理温度的升高明显增强,Er3+的上转换发光出现明显的Stark分裂现象,这亦说明Er3+已进入到GdF3纳米晶相中。通过研究上转换发光强度与泵浦功率的关系,确定绿光上转换发光为双光子过程。     

970nm抽运下Er3+/Yb3+/Tm3+共掺碲酸盐玻璃的发光特性

研究了Er3+/Yb3+共掺、Tm3+/Yb3+共掺、Er3+/Yb3+/Tm3+共掺碲酸盐玻璃在970nm抽运下的荧光光谱和上转换光谱性质，测试了Er3+离子的4I11/2和4I13/2能级荧光寿命变化情况.结果发现Er3+/Yb3+/Tm3+共掺碲酸盐玻璃的常规荧光谱线在1450—1700nm区域明显加宽，并在1630nm有一荧光峰，可能是Tm3+：1G4→3F2跃迁产生.上转换发光研究表明，由于碲酸盐玻璃声子能量低的缘故，三种共掺系统下都存在上转换发光现象.在Er3+/Yb3+/Tm3+共掺中，上转 关键词： Er3+/Yb3+/ Tm3+共掺 碲酸盐玻璃 荧光 上转换光谱     

Tm3+/Yb3+共掺杂玻璃和玻璃陶瓷中蓝色 上转换发光中的能量传递过程

利用高温固相法制备了Tm³⁺/Yb³⁺共掺杂的氟氧化物玻璃和玻璃陶瓷材料,在980 nm的激光激发下,样品发射出明亮的蓝色上转换荧光。通过对玻璃和玻璃陶瓷样品的对比,发现Tm³⁺离子和Yb³⁺离子之间存在着Tm³⁺(³H₄)→Yb³⁺(²F_5/2)的反向能量传输通道,并且与晶场有较强的依赖关系。分析了在玻璃和玻璃陶瓷中蓝色上转换发光过程,随着敏化剂Yb³⁺浓度的增加,在玻璃中正向和反向能量传递的竞争作用使得Tm³⁺离子在Yb³⁺离子的最佳浓度时上转换发光最强;而在玻璃陶瓷中, Tm³⁺离子的上转换发光始终随着Yb³⁺离子的浓度增加而增强。     

Investigation of up-conversion luminescence properties of RE/Yb co-doped Y2O3 transparent ceramic (RE=Er, Ho, Pr, and Tm)

RE/Yb co-doped Y₂O₃ transparent ceramics (RE=Er, Ho, Pr, Tm) were fabricated and characterized from the point of up-conversion luminescence. All the samples exhibit high transparence not only in near-infrared band (NIR) band but also in visible region, which ensures the output of the up-conversion luminescence. Under 980 nm excitation, green and red emissions were observed in Er, Yb:Y₂O₃ transparent ceramic, while green emission was detected in Ho, Yb and Pr, Yb co-doped Y₂O₃ transparent ceramics. In Tm, Yb co-doped Y₂O₃ ceramic, very intense blue up-conversion luminescence was detected. The dependence of up-conversion emission intensity on the pumping power was measured for each RE/Yb co-doped Y₂O₃ transparent ceramic, and the up-conversion mechanism was discussed in detail. Meanwhile, the energy transfer efficiency was calculated.     

掺Er3+/Yb3+氟氧玻璃的上转换发光特性

制备了新的Er³⁺/Yb³⁺共掺氟氧硅酸盐微晶玻璃,测试了材料的荧光光谱和吸收光谱。上转换光谱表明:有红(645 nm)、绿(545,522 nm)、蓝(480 nm)4个发光中心,分别对应Er³⁺的⁴F_9/2→⁴I_15/2、⁴S_3/2→⁴I_15/2、²H_11/2→⁴I_15/2、⁴F_7/2→⁴I_15/2 跃迁。发光曲线拟合斜率分别为1.81、2.39、1.95、2.15,均为双光子吸收过程。样品经热处理降低了声子能量,大大提高了上转换效率。采用Judd-Ofelt理论对样品光谱进行了分析,拟合得到了强度参数。     

Er~(3+)/Eu~(3+)及Yb~(3+)/Er~(3+)/Eu~(3+)共掺杂硼硅酸盐玻璃的上转换发光分析

采用高温固相烧结法制备了Er3+/Eu3+共掺杂和Yb3+/Er3+/Eu3+共掺杂系列硼硅酸盐玻璃样品。在978 nm半导体激光器抽运下,测量了样品的光致发光谱,分析了上转换机制。结果表明:随着Er3+浓度的增加,Eu3+的595 nm光谱强度增强;Eu3+的692 nm光谱强度随Yb3+浓度增加而增强,并明显强于595 nm光谱。Er3+/Eu3+、Yb3+/Eu3+之间的能量传递和合作上转换等机制导致Eu3+离子上转换发射。     

Tm3+ ,Yb3+共掺微晶玻璃蓝色上转换荧光的温度特性

制备了Tm³⁺,Yb³⁺共掺氟氧化物微晶玻璃, 在980 nm二极管激光器泵浦下研究了其上转换发光。发现将前驱玻璃进行热处理后,源于Tm³⁺的¹G₄能级到基态³H₆跃迁所产生的蓝色上转换荧光在463 nm和476 nm出现明显劈裂。在此基础上分析了该劈裂蓝色上转换荧光在303~623 K范围内的温度特性。结果表明:Tm³⁺,Yb³⁺共掺氟氧化物微晶玻璃蓝色上转换荧光可应用于光学测温,其测温最大灵敏度为4.2×10^-4 K^-1,相应温度为352 K。     

Tm3+和Er3+共掺杂氟氧化物玻璃陶瓷材料结构和上转换发光性质的研究

报道了一种新的上转换氟氧化物玻璃陶瓷材料,组份为65GeO2-25NaF-10BaF2(MFG)。研究了Tm^3 和Er^3 共掺MFG玻璃陶瓷中的发光性质。通过X射线衍射和Raman散射分析了MFG玻璃陶瓷的结构性质。分别测量了Tm^3 和Er^3 共掺MFG玻璃及玻璃陶瓷和Er^3 单掺MFG玻璃中的红外发射谱（λex=488nm)和上转换发射谱（λex=978nm)。给出了稀土离子掺入微晶的证据;（1）和MFG：1mol%Tm^3 、2mol%Er^3 玻璃相比,在978nmLD激发下,MFG：1mol%Tm^3 、2mol%Er^3玻璃陶瓷中红色上转换发光大大增强,红不与绿光的比值大大提高。（2）在488nm激光激发下,玻璃陶瓷样品中Tm^3 离子1．7μm左右的发射光谱明显窄化。最后讨论了玻璃陶瓷这种结构上转换发光的影响和其在上转换发光及光通信中的应用潜力。     

Er3+-Yb3+-Tm3+共掺CdF2:PbF2基玻璃中的荧光特性及其上转换机制

在 98 0nm半导体激光激发下 ,在Er3 Yb3 Tm3 共掺玻璃样品中得到了如下的 5条较强的上转换荧光带 ,分别是近红外 (80 0nm) ,红 (6 4 5nm) ,绿 (5 4 5和 5 2 5nm) ,蓝 (4 80nm)及紫 (4 0 7nm)。与Er3 Yb3 共掺样品相比 ,Tm3 的加入使得 4 80nm的蓝光显著增强 ,这应与Tm3 特殊的能级结构有关 ;荧光强度随激发功率变化的双对数曲线表明 4 80nm蓝光发射是双光子激发过程 ,为两个Yb3 的合作上转换敏化发光 ,随着激发功率的增加 ,4 80nm荧光的logI logP曲线的斜率将变小 ,逐渐向下“弯曲”。作者详细的分析了各条荧光带的上转换机制 ;并用速率方程讨论了稳态情况下 4 80nm蓝色上转换荧光强度随激发功率变化的关系 ,其结果与实验一致。