Spectroscopic properties and mechanism of Tm^(3+)/Er^(3+)/Yb^(3+) co-doped oxyfluorogermanate glass ceramics containing BaF_2 nanocrystals

Transparent Tm^3＋/Er^3＋/yb^3＋ co-doped oxyfluorogermanate glass ceramics containing BaF2 nanocrystals are prepared. Under excitation of a 980-nm laser diode （LD）, compared with the glass before heat treatment, the Tm^3＋/Er^3＋/yb^3＋ co-doped oxyfluorogermanate glass ceramics can emit intense blue, green and red up-conversion luminescence and Stark- split peaks; X-ray diffraction （XRD） and transmission electron microscope （TEM） results show that BaF2 nanocrystals with an average diameter of 20 nm are precipitated from the glass matrix. Stark splitting of the up-conversion luminescence peaks in the glass ceramics indicates that Tm^3＋, Er^3＋ and （or） Yb^3＋ ions are incorporated into the BaF2 nanocrystals. The up-conversion luminescence intensities of Tm^3＋, Er^3＋ and the splitting degree of luminescence peaks in the glass ceramics increase significantly with the increase of heat treat temperature and heat treat time extension. In addition, the possible energy transfer process between rare earth ions and the up-conversion luminescence mechanism are also proposed.

Intense up-conversion emissions of yb3＋/Dy3＋ co-doped A12O3 nanopowders prepared by non-aqueous sol-gel method＊

yb3＋/Dy3＋ co-doped A1203 nanopowders have been prepared by the non-aqueous sol-gel method and their up- conversion photoluminescence spectra are measured under excitation by a 980-nm semiconductor laser. The results show that there are comparatively abundant spectra of up-conversion emissions centered at 378, 408, 527 and 543, and 663 nm, corresponding to 4C9/2→ 6H13/2, 4C9/2→ 6Hll/2, 4115/2 → 6H13/2, and 4F9/2 →6Hll/2 transitions of Dy3＋, respectively. Two-photon and three-photon processes are involved in ultraviolet, violet, green, and red up-conversion emissions. The energy transition between Yb3＋ and Dy3＋ is discussed.

Enhancement in Laser Performance of Er^(3+)/Yb^(3+) Co-doped Phosphate Glass Materials

Er3＋/Yb3＋co-doped phosphate are presented, laser glass materials with composition of P2O5-A12O3-Ba CO3-KNO3-Li2O-Zn O-Er2O3-Yb2O3（R-PABKLZ） are presented, in which an optimal molar ratio of 1：4 between Er3＋ and Yb3＋ was observed for achieving peak laser gain. Furthermore, due to adding 4.7 mol% Li1＋ and 4.6 mol% Zn2＋ ions into the glass, an optimum composition structure based laser material was demonstrated. On the other hand, since the high temperature melting method with changeable temperature control was used, the emission cross section of fl uorescence, excited lifetime, and an effective spectral half width reached 9.70 × 10-21 cm2, 8.20 ms, and 53.16 nm, respectively, so that a laser gain（semi× rad） of 103.05 was obtained, which is signifi cantly higher than previously reported results. The manuscript also argued the mechanism of relevant laser gain improvement.

Spectroscopy and Energy Transfer in Yb^(3+) and Tm^(3+) Co-doped Gd_3Ga_5O_(12) Crystal

Yb3＋/Tm3＋ co-doped Gd3Ga5O12 single crystal with a dimension of Φ30mm×20mm was grown successfully by Czochralski method.The absorption spectrum was recorded at room temperature and used to calculate the absorption cross-section.Based on the Judd-Ofelt（J-O） theory,we obtained the three intensity parameters and spectral parameters of this crystal,such as the line strengths,oscillator strengths,radiative probabilities and radiative lifetimes as well as the fluorescent branching ratios.Room temperature fluorescence spectra and luminescence decay curves were recorded.The energy transfer between Yb3＋-Tm3＋ was observed and the mechanism was discussed.The stimulated emission cross-section of the 3F4→3H6 transition was calculated by the Füchtbauer-Ladenburg（F-L） equation.The potential laser gains for this transition were also investigated.This crystal is promising as a tunable infrared laser crystal at 2.0 μm.

水热法合成NaYF_4∶Yb^(3+)-Er^(3+)及其上转换发光性质

采用水热法合成了不同浓度Yb^(3+)和Er^(3+)共掺NaYF_4上转换发光材料。利用X-射线粉末衍射技术鉴定了物相的纯度,结果表明,样品的XRD与NaYF_4(JCPDS 28-1192)标准卡片一致,均为纯相,结晶度高。在扫描电镜的辅助下,对样品的形貌进行了表征分析,其微观形貌呈六方棱柱状,柱长7μm左右,直径3μm左右,且尺寸分布均匀。在此基础上,利用荧光分光光度计(激发光源为980 nm激光器)对样品的发光性能进行了测试,在980 nm激光器的激发下,得到了发射峰位分别位于525 nm、550 nm、660 nm组成的上转换光谱,可指认为Er^(3+)的2H11/2,4S3/2→4I15/2(绿光)和4F9/2→4I15/2(红光)跃迁。进一步讨论了样品发光强度和泵浦源功率之间的关系,发现绿光和红光发射均为双光子过程。

SrZrO3:Er,Yb荧光粉的上转换发光特性研究

采用高温固相法制备出SrZrO3∶Er,Yb上转换发光材料,用XRD、拉曼光谱和荧光光谱对其结构和上转换荧光特性进行表征和分析。XRD和拉曼光谱结果表明,得到的SrZrO3∶Er,Yb为正交相结构。980nm激发下,SrZrO3∶Er荧光粉存在较强的上转换发光,在533nm、557nm和688nm处存在两个绿色发射带和一个红色发射带,Yb^3+的掺杂能够显著提高其上转换发光效率。SrZrO3∶Er,Yb中Er^3+的猝灭浓度为1.0%,Yb^3+的猝灭浓度为15%。通过研究发光强度随激发功率的关系,探究了Er^3+和Yb^3+双掺杂体系的发光机制,证实533nm、557nm处的绿光发射以及688nm处的红光发射都是双光子过程。

Structural and optical studies of Yb^(3+),Er^(3+) and Er^(3+)/Yb^(3+) co-doped phosphate glasses

Phosphate glass samples with various Yb2O3 and Er2O3 contents were synthesized by the conventional melt quenching technique and characterized by X-ray diffraction, IR absorption spectroscopy and Raman scattering spectroscopy. The absorption, emission spectra and fluorescence decay studies were carried out both at low and room temperatures. Results showed the existence of several sites occupied by the rare earth ions in the phosphate glass. Up-conversion and cooperative fluorescence were also discussed.

Emissions of Er3+ and Yb3+ co-doped SrZrO3 nanocrystals under near-infrared and near-ultraviolet excitations

In this study,the upconversion(UC)emissions of Er3+and Yb3+co-doped SrZrO3 nanocrystals(NCs)were investigated in terms of the thermal annealing temperature and concentration of Er3+ions and compared with the emissions under a near-ultraviolet(near-UV)excitation.The NCs were synthesized by the combustion method,and the as-synthesized NCs were post-annealed at high temperatures.The X-ray diffraction patterns revealed that the grain sizes and crystallinity degrees of the samples increased with increasing annealing temperatures.The photoluminescence spectra of our samples exhibited strong green and very weak red emissions with the near-UV excitation,originating from the f-f transitions in the Er3+ions.Interestingly,under near-infrared(near-IR)excitation,we identified sizable visible emissions at 525,547,and 660 nm in our NCs,which indicated that the UC process successfully occurred in our NCs.These UC emissions were maximized in the NCs with an Er3+concentration of 0.02 and thermal annealing at 1000°C.We found that the intensity ratios of red to green emissions increased with increasing annealing temperatures.We discussed the differences in the emissions between near-UV and near-IR excitations.

Up-conversion luminescence of Tm^(3+)/Yb^(3+) co-doped oxy-fluoride glasses

The oxy-fluorosilicate glasses co-doped with Yb3+/Tm3+ were prepared.The absorption spectra were recorded.The Tm3+ ion showed two absorption bands,with one at 774 nm due to 1G4→3H6 transition and the other at 667 nm due to 1G4→3F4 transition.The energy transfer between Tm3+ ion and Yb3+ ion and the up-conversion fluorescence of Tm3+ ion were investigated using 980 nm LD excitation.The results showed that the blue and red emissions were three-photon absorption processes corresponding with 1G4→3H6 and 1G4→3F4...

一锅法制备YF_3:Yb^(3+)-Er^(3+)纳米晶复合PNIPAm-co-PAA纳凝胶及其荧光温敏行为

采用巯基乙胺为配体,以硝酸铒(Er(NO3)3),硝酸镱(Yb(NO3)3),硝酸钇(Y(NO3)3)和氟化铵(NH4F)为原料,水热法制备表面含NH2基团的活性YF3:Yb3+-Er3+纳米晶;以过硫酸钾(K2S2O8)为引发剂,借助1-乙基-(3-二甲基氨基丙基)碳酰二亚胺(EDC)与N-羟基丁二酰亚胺(NHS)的偶联反应,在活性纳米晶存在下,进行N-异丙基丙烯酰胺(NIPAm),N,N'-亚甲基双丙烯酰胺(BIS)与丙烯酸的自由基共聚合,一锅法制备了YF3:Yb3+-Er3+/PNIPAm-co-PAA荧光温敏纳凝胶.对制备的纳米晶及纳凝胶的结构与荧光性能进行了表征.结果表明,纳米晶的粒径为6~10 nm,呈单分散分布;纳凝胶的粒径呈多分散分布,粒径主要分布在100~300 nm.PL光谱分析表明,活性YF3:Yb3+-Er3+纳米晶的4F7/2→4I15/2跃迁,在483和496 nm处产生明显的能级劈裂;纳凝胶中,该能级劈裂依然存在,但随温度升高发生耦合;环境温度对纳凝胶的上转换发光强度产生明显影响.

Nd^(3+)/Yb^(3+) co-doped mid-infrared luminescence fluorobromide glass with energy transfer and zero-thermal-quenching IR emission

Nd^(3+)/Yb^(3+)co-doped fluorobromide glass samples were prepared by melt quenching.The mid-infrared(MIR)luminescence of the Nd^(3+)/Yb^(3+)co-doped fluorobromide glass was investigated by Br-doping reduces the phonon state density of the matrix.The 3.9μm MIR luminescence of the samples excited at 793 and 980 nm pump excitation was investigated in detail.There is an effective mutual energy transfer process between Nd^(3+)and Yb^(3+).It is proved under 793 nm excitation that the luminescence of Nd^(3+)at 3.9μm is reduced by effective energy transfer from,Nd^(3+):2 H11/2→Yb^(3+):2 F5/2,At the same time,it is proved that the effective energy transfer from Yb^(3+):2 F5/2→Nd^(3+):2 H11/2 under the excitation of 980 nm enhances the luminescence of Nd^(3+)at 3.9μm.In addition,it is found that the samples still have good infrared(IR)luminescent properties when the temperature changes.The emission cross-sectional area and the absorption cross-sectional area areσem(3.87×10^(-20)cm^(2))andσabs(4.25×10^(-20)cm^(2)).The fluorescence decay characteristics of the sample at 3.9μm at the 2 H11/2 level were investigated and the fluorescence lifetime was calculated.The gain performance of the sample was calculated and analyzed,which can reach 4.25×10^(-20)cm^(2).Those results prove that Nd^(3+)/Yb^(3+)co-doped fluorobromide glass is the potential mid-infrared laser gain material.

Silver nanoparticles enhanced near-infrared luminescence of Er^3＋/Yb^3＋ co-doped multicomponent phosphate glasses

A new way to improve the 1.53μm emission in Er3＋/Yb3＋ co-doped multicomponent phosphate glass was demonstrated by introducing silver nanoparticles （NPs） in rare-earth doped glass. The existence of Ag NPs was confirmed by absorption spectra and transmission electron microscopy （TEM） measurements. The homogeneous distribution of silver NPs could be observed by the TEM images. UV-Vis-NIR absorption spectra revealed that the surface plasmon band was centered at about 420 nm. The photoluminescence spectra of glass samples were used to investigate the effect of silver NPs on the fluorescence properties of Er3＋. Efficient 1.53μm emis-sion was obtained in prepared samples when pumped at 980 nm laser diode （LD）. The 1.53μm emission intensity could be enhanced 87% by doping 2 mol.% AgCl due to the increased localized field effect in the vicinity of NPs and the possible energy transfer from silver NPs to Er3＋ions. Our present work may point out one way to enhance the gain coefficient of Er3＋/Yb3＋ co-doped glass fiber.

Effect of concentration quenching on the spectroscopic properties of Er^(3+)/Yb^(3+) co-doped AlF_3-based glasses

A series of highly Er^(3+)/Yb^(3+) co-doped fluoroaluminate glasses have been investigated in order to develop a microchip laser at 1.54 μm under 980 nm excitation. Measurements of absorption, emission and upconversion spectra have been performed to examine the effect of Er^(3+)/Yb^(3+) concentration quenching on spectroscopic properties. In the glasses with Er^(3+) concentrations below 10 mol%, concentration quenching is very low and the Er^(3+)/Yb^(3+) co-doped fluoroaluminate glasses have stronger fluorescence of 1.54μm due to the ~4I_(13/2)→~4I_(15/2) transition than that of Er^(3+) singly-doped glasses. As Er^(3+) concentrations above 10 mol% in the Er^(3+)/Yb^(3+) co-doped samples, concentration quenching of 1.54μm does obviously occur as a result of the back energy transfer from Er^(3+) to Yb^(3+). To obtain the highest emission efficiency at 1.54μm, the optimum doping-concentration ratio of Er^(3+)/Yb^(3+) was found to be approximately 1:1 in mol fraction when the Er^(3+) concentration is less than 10 mol%.

纳米Yb^(3+)-Er^(3+)/TiO_2的制备及其在降解染料废水中的应用

为提高TiO_2的催化活性,采用溶胶凝-胶法合成了不同Yb^(3+)和Er^(3+)掺杂量,不同焙烧温度的Yb3+-Er3+/TiO_2光催化剂,并对所制得的样品进行了FT-IR、XRD、SEM表征,用亚甲基蓝溶液模拟有机染料废水,来测试样品的催化性能.结果表明:所得粉体均为锐钛矿的TiO_2,稀土Yb^(3+)、Er^(3+)掺杂TiO_2能细化晶粒;摩尔比n(Yb^(3+)-Er^(3+)):n(TiO_2)=2%的样品在400℃焙烧,无需灯源照射,常温常压不通氧气条件下,加入1mL氧化剂30%的H2O2,降解10mg.L-1亚甲基蓝溶液6h,降解率可达95%.

Influence of Gd_2O_3 and Yb_2O_3 Co-doping on Phase Stability,Thermo-physical Properties and Sintering of 8YSZ

The role of multicomponent rare earth oxides in phase stability, thermophysical properties and sintering for ZrO2-based thermal barrier coatings （TBCs） materials is investigated. 8YSZ codoped with 3 mol% Gd2O3 and 3 mol% Yb2O3 （GYb-YSZ） powders are synthesized by solid state reaction for 24 h at various temperatures. As temperature increases, stabilizers are dissolved into zirconia matrix gradually. Synthesized at 1 500 °C, GYb-YSZ is basically composed of cubic phase. GYb-YSZ exhibits excellent phase stability and sinters lower than 8YSZ by nearly three times. The thermal conductivity of GYb-YSZ is much lower than that of 8YSZ, and the thermal expansion coefficient of GYb-YSZ is comparable to that of 8YSZ. The influence of Gd2O3 and Yb2O3 co-doping on phase stability, thermal conductivity and sintering of 8YSZ is discussed.

An investigation on the magneto-optic properties of terbium gallium garnet under high magnetic field

This paper reports that a series of Nd3＋：Er3＋：yb3＋ co-doped borosilicate glasses have been prepared and their absorption spectra measured. The J-O intensity parameters Ωk （k = 2, 4, 6）, spontaneous radiative lifetime Trad, spontaneous transition probability A, fluorescence branching ratio β and oscillator strength fed of the Nd3＋ ions at room temperature are calculated based on Judd-Ofelt （J-O） theory. The temperature dependence of the up-conversion photoluminescence characteristics in a Nd3＋：Er3＋：Yb3＋ co-doped sample is studied under a 978 nm semiconductor laser excitation, and the energy transfer mechanisms among Yb3＋, Er3＋ and Nd3＋ ions are analysed. The results show that the J-O intensity parameters Ω2 increase when the Nd3＋ concentration of the Nd3＋：Er3＋：yb3＋ co-doped borosilicate glasses increases. The possibility of spontaneous transition is small and lifetimes are long at levels of 4F5/2 and 4F3/2. The intensity of Nd3＋ emissions at 595, 691, 753, 813 and 887 nm axe markedly enhanced when the sample temperature exceeds 400 K. The reasons being the cooperation of the secondary sensitization from Era＋ to Nd3＋ and the contribution of a multi-phonon.