Optical transitions in Er^3＋ doped lead germanate glasses

Er^{3+}- and Er^{3+}/Yb^{3+}-doped lead germanate glasses that are suitable for use in fibre lasers and optical amplifiers as well as optical waveguide devices have been fabricated and characterized. The absorption spectra from near-infrared to visible were obtained and the Judd－Ofelt parameters were determined from the absorption band. Intense and broad 1.53μm infrared fluorescence and visible upconversion luminescence were observed under 976 nm diode laser excitation. For 1.53μm emission band, the full widths at half-maximum are 36, 37, 51 nm for GPE, GPYE and GPFE samples, respectively. For frequency upconversion emission, the intense bands centred at around 524, 545, 657nm are due to the {}^4S_{3/2}+{}^2H_{11/2}→{}^4I_{15/2} and {}^4F_{9/2}→{}^4I_{15/2} transitions of Er^{3+} ions. The quadratic dependence of the green and red emissions on excitation power indicates that the two-photon absorption process occurs under the 976nm excitation.     

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。     

Comprehensive research about the cooperative up-conversion luminescence of the ytterbium-doped oxyfluoride vitroceramics

The cooperative up-conversion blue luminescence of Yb^{3+} ion-doped oxyfluoride vitroceramic material (Yb:FOV) and the influence of co-doped Ho^{3+} ion, when excited by a 960 nm diode-laser, are studied in this paper. A strong blue 479.1 nm up-conversion luminescence of the Yb:FOV material is discovered. It is found that the 479.1 nm luminescence results from the cooperative up-conversion of the coupled states of the Yb^{3+}－Yb^{3+} clusters formed by two adjacent Yb^{3+} ions. The measured cooperative up-conversion luminescence main peak 479.1 nm of this paper is different from the characteristic fluorescence main peak of the Tb^{3+} ion positioned at about 495－504 nm wave-range. Our result coincides with all the published correct papers, whose cooperative up-conversion luminescence main peaks of the direct Yb^{3+}－Yb^{3+} clusters are all positioned at about 476－480 nm wave-range. All of these indicate that the large cooperative up-conversion blue luminescence of the direct Yb^{3+}－Yb^{3+} clusters discovered in this paper is stable. It further proves that the cooperative up-conversion green luminescence may result from the Yb^{3+}-Tb^{3+} cooperative effect. In particular, the original work of this paper improves considerably on the traditional concept by the experimental facts that the blue 479.1 nm cooperative up-conversion luminescence strength of Yb(5):FOV is 230 times greater than that of fluoride glass Yb(3):ZBLAN. This is a great development to meet the practical requirements for blue up-conversion luminescence strength. This result indicates that the large cooperative up-conversion blue luminescence could be achieved excellently by using a suitable material, such as oxyfluoride vitroceramic, which provides a better chance to form better Yb^{3+}－Yb^{3+} clusters and has less relaxation to keep the more efficient up-conversion luminescence. It is also found that impurities seriously reduce the cooperative up-conversion luminescence intensity due to the cross-relaxation from the Yb^{3+}－Yb^{3+} clusters, which means that the cooperative up-conversion blue luminescence could be further improved by pure Yb^{3+} ion-doped materials that have as few impurities as possible to reduce the cross-relaxation. The large cooperative up-conversion blue luminescence of Yb(5):FOV also comes from its higher concentration (5 mol%) of activator Yb^{3+} ion which acts well because the cooperative up-conversion blue luminescence intensity varies linearly against the square of the concentration of Yb^{3+} ions in the range of 0.5－5 mol%. In summary, the great improvement of our work on cooperative up-conversion blue luminescence results from the comprehensive enhancement of the factors of better-coupled chance of the Yb^{3+}－Yb^{3+} clusters, less cross-relaxation, better concentration contribution of Yb^{3+} activator, non-saturation, and better up-conversion luminescence efficiency.     

Comparative study of spectroscopic properties of Er^3＋／Yb^3＋-codoped tellurite glass and fibres under 980nm excitation＊

A tellurite fibre of TeO_{2}－ZnO－La_{2}O_{3}－Li_{2}O glass codoped with 20000 ppm ytterbium and 5000 ppm erbium was fabricated by the suction casting and rod-in-tube technologies. The absorption spectrum of Er^{3+}/Yb^{3+} -codoped bulk glass has been measured. From the Judd－Ofelt intensity parameters, the spontaneous emission probability and radiative lifetime τ_{rad} of Er^{3+}:{}^{4}I_{13/2}→{}^{4}I_{15/2} transition for the bulk glass have been calculated. The emission fluorescence spectra and lifetimes around 1.5μm, and subsequent upconversion fluorescence in the range of 500－700nm were measured in fibres and compared with those in bulk glass. The changes in amplified spontaneous emission with fibre length and pumping power was also measured. It was found that the emission spectrum from erbium in fibres is almost twice as broad as the corresponding spectrum in bulk glass when pumped at 980nm.     

Analysis of the laser performance of Tm3+, Tb3+(Ho3+):YVO4 crystals at ～1.5μm wavelength

The absorption spectra of Tb,Tm:YVO_4 and Ho,Tm:YVO_4 are measured. The radiant and non-radiant transition probabilities from higher level to lower level, A_{i,j} and ω_{i,j}, and the cross-elaxation probability are calculated in virtue of Judd－Ofelt and Dexter theories. The fluorescence lifetime of Tm^{3+} in the Tb^{3+} (or Ho^{3+}) co-doped crystal is calculated. It indicates that the lifetime of initial level {}^3H_4 of the laser transition can be shorter than that of terminal level {}^3F_4 of the transition if the atomic percentage of Tb^{3+} (or Ho^{3+}) ions is bigger than about 1 at%: namely, by means of the co-doping Tb^{3+} (or Ho^{3+}) ions the self-termination phenomenon of laser light can be eliminated. Inserting the optic parameters to the formula deduced here on the laser threshold power P^{(4)}_{th} and the slope efficiency η^{(4)}_s of the four-energy-level system, we obtain the relationship of threshold power P^{(4)}_{th} to the concentration of Tm^{3+} ions and discuss the effect of Tb^{3+} (or Ho^{3+}) ion concentration on the laser threshold power P^{(4)}_{th} around 1.5μm wavelength. The result shows that Tb,Tm:YVO_4 crystal is a better choice to make the laser at ～1.5μm wavelength than Ho,Tm:YVO_4 crystal. We give the appropriate composition of (1－2) at% Tb, (1－2) at% Tm:YVO_4, just for reference.     

The mechanism research of the Cr^4＋Nd^3＋：YAG laser

The 946nm diode-pump microchip self-Q-switched laser of a chromium and neodymium codoped yttrium aluminum garnet crystal material (Cr^{4+}Nd^{3+}:YAG) is studied, especially about its physical mechanism of operation. The {}^4F_{3/2}→{}^4I_{9/2} transition of Nd^{3+} ion is beneficial to achieving laser oscillation in a quasi-three-level system based on coating the cavity mirrors of the microchip with films that suppress the 1064nm operation and enhance the 946nm laser. The Cr^{4+} ion is a saturable absorber. The initial loss N_{t1} is high, which acts as the threshold for laser oscillation. The stable loss N_{t2} is low because the Cr^{4+} ion is acceleratively bleached by the fast enhancement of the oscillating laser. The high N_{t1}, small N_{t2} and fast progresses permit the oscillating laser of the Cr^{4+}Nd^{3+}:YAG to have a good self-Q-switched property whose full width at half maximum is about 4.2ns. Its highest laser power is about 5.7mW. Its peak power is about 150W. Its good fundamental transverse TEM_{00} mode results from the absorption bleaching established by both the pump and oscillating lasers, which suppress other transverse mode and allow the oscillation only in the fundamental transverse TEM_{00} mode.     

Er~(3+)/Yb~(3+)共掺杂氧氟硼硅酸盐微晶玻璃绿色上转换发光的温度特性

采用高温熔融法和热处理工艺制备得到透明的Er3+/Yb3+共掺杂氧氟微晶玻璃。XRD结果证实析出的纳米晶相为Ba YF5。在980 nm激发下,观察到强的绿光发射,源于Er3+的2H11/2→4I15/2和4S3/2→4I15/2跃迁的上转换发光。根据荧光强度比(FIR)的方法研究了微晶玻璃上转换荧光的温度传感特性,其最大灵敏度在523 K时为0.003 4 K-1,表明Er3+/Yb3+共掺氧氟硼硅酸盐微晶玻璃上转换发光在高精度温度传感器方面具有一定的应用前景。     

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.     

Ultraviolet and visible upconversion dynamics in Er^3＋：YAlO3 under ^2H11/2 excitation

The luminescence of Er^3＋：YAlO3 in ultraviolet visible and infrared ranges under the 518 nm excitation of the multiples ^2H11/2 have been investigated. Ultraviolet （275 nm and 318 nm）, violet （405 nm and 413 nm） and blue （474 nm） upconversion and infrared downconversion luminescence has been observed. By means of measuring the fluorescence decay curves and using the theory of rate equations, the luminescence kinetics was studied in detail and the processes of energy transfer upconversion （ETU） and excitation state absorption （ESA） were proposed to explain the upconversion phenomena.     

Intense Green Upconversion Luminescence in Er^3＋：Yb^3＋ Codoped Fluorophosphate Glass Ceramic Containing SrTe5O11 Nanocrystals

Er^3＋ ：Yb^3＋ codoped tellurite-fluorophosphate （TFP） glass ceramic exhibits much stronger upconversion luminescence. The intensity of the 540nm green light and 651 nm red light of the TFP glass ceramic is 120 times and 44 times stronger than that of the fluorophospahte （FP） glass, respectively. XRD analysis shows that the nanocrystal in TFP glass ceramic is SrTe5O11. TFP glass ceramic also displays much higher upconversion fluorescence lifetime and crystallization stability. The narrow and strong peak at 540nm is very ideal for practical upconversion luminescence realization. This work is a new trial for exploring non-PbF2 involved nanocrystal upconversion glass ceramics.     

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.     

Optical transitions and upconversion properties of Er^3＋-doped chloride tellurite glasses

Er^{3+}-doped lead chloride tellurite glasses were prepared using the conventional melting and quenching method. The absorption spectra were measured and the Judd－Ofelt analysis was performed. The spectroscopic parameters such as the intensity parameters, transition probabilities, radiative lifetimes, and branching ratios were obtained. Intense infrared emission and visible upconversion luminescence under 976 nm excitation were observed. For the 1.55μm emission, the full width at half maximum and the emission cross sections are more than 50 nm and 8×10^{- 20}cm^2, respectively. Three efficient visible luminescences centred at 525, 547, and 658nm are assigned to the transitions from the excited states {}^{2}H_{11/2}, {}^{4}S_{3/2}, and {}^{4}F_{9/2} to the ground state {}^{4}I_{15/2}, respectively. The upconversion mechanisms and the power-dependent intensities are also discussed and evaluated.     

铒离子在氟氧化物玻璃陶瓷中的上转换发光特性研究

用转移函数方法分析了Er^3 在铒镱共掺杂的氟氧化物玻璃陶瓷中的上转换发光过程,Er^3 绿色辐射的上转换发光强度与泵浦激光功率的非平方关系是由于Er^3 和Yb^3 之间的强交叉驰豫过程引起的,讨论了在稀土离子共掺杂的氟氧化物玻璃陶瓷中提高Er^3 的上转换发光强度的几种方法。     

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。     

Spectroscopic properties and mechanism of Tm^3＋/Er^3＋/Yb^3＋ co-doped oxyfluorogermanate glass ceramics containing BaF2 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.     

NaGd(WO 4)2∶Yb^3+,Ho^3+,Cr^3+微米晶的上转换发光与温度特性

采用水热法制备了NaGd(WO4)2(NGW)∶Yb^3+,Ho^3+,Cr^3+微米晶。研究了Cr^3+离子掺杂浓度对样品的晶体结构、微观形貌、上转换发光及温度传感特性的影响。在980 nm激光激发下,所有样品均发射以546 nm为中心的较弱绿光和以660 nm为中心的强红光,分别对应于Ho^3+离子的5F4,5S2→5I8和5F5→5I8能级跃迁。随Cr^3+离子掺杂量增加,绿光发射峰强度逐渐减弱,而红光发射先增大后减小,在10%时达到最大,样品色坐标逐渐向红色区域偏移。样品的变温光谱表明,NGW∶Yb^3+,Ho^3+,10%Cr^3+微米晶具有很好的温度特性,其测温灵敏度在486 K时达到最大,约为0.0337 K^-1,比NGW∶Yb^3+,Ho^3+的灵敏度提高近1倍。     

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。     

Research on upconversion luminescence in new Er3+/Yb3+codoped oxyfluoride borosilicate glass ceramics

The upconversion luminescence of Er3+/Yb3+ ions is researched in a novel transparent oxyfluoride borosil icate glass and glass ceramics under 980-nm excitation.Fluoride nanocrystals Ba2 YF7 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 Er3+/Yb3+ codoped transparent glass-ceramics.which may be due to the variation of coordination environment around Er3+ and Yb3+ ions after crvstallization.The possible upconversion mechanism is also discussed.     

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。     

Luminescence of Ba0.85MgAl10O16.94：Eu^2＋0.09 with different fluxes

BaMgAl10O17:Eu^2 , known as BAM, is a very important blue-emitting phosphor used in plasma display panels (PDP) and three band fluorescent lamps. In this paper, the Ba0.s5MgAl10O16.94:Eu^2 0.09 phosphors with different fluxes (BaF2, MgF2, AIF3, BaCl2, MgCl2, AICl3, H3BO3) were prepared by high temperature solid-state reaction method and the influence of different fluxes on the luminescence of Ba0.85MgAl10O16.94:Eu^2 0.09 phosphor was studied under 254nm excitation and vacuum ultraviolet (VUV) excitation. It was found that fluorides have better flux effects than chlorides and H3BO3. The mechanism of particle growth in the presence of flux in the process of phosphor preparation is discussed in detail. Particle size distribution and the crystal structure of the phosphors are also analysed.