Upconversion properties of Er3+, Yb3+ and Tm3+ codoped fluorophosphate glasses

Er3+, Yb3+ and Tm3+ codoped fluorophosphate glasses emitting blue, green and red upconversion luminescence at 970 nm laser diode excitation were studied. It was shown that Tm3+ behaves as the sensitizer to Er3+ for the green upconversion luminescence through the energy transfer process: Tm 3+:H-3(4) + Er3+:I-4(15/2) -> Er3+:I-4(9/2) + Tm3+:H-3(6), and for the red upconversion luminescence through the energy transfer process: Tm3+:F-3(4) + Er3+:I-4(11/2) -> TM3+:H-3(6) + Er3+:4 F-9/2. Moreover, Er3+ acts as quenching center for the blue upconversion luminescence of TM3+. The sensitization of Tm3+ to Er3+ depends on the concentration of Yb3+. The intensity of blue, green and red emissions can be changed by adjusting the concentrations of the three kinds of rare earth ions. This research may provide useful information for the development of high color and spatial resolution devices and white light simulation. (C) 2006 Elsevier B.V. All rights reserved.

X 射线转换屏用Tb3+激活磷酸盐发光玻璃

Phosphate glasses 60P2O5-15CS2O- 15Al2O3-10BaO were made by high temperature melt-annealing method. The absorption spectra, excitation spectra and emission spectra of Gd³⁺-Tb³⁺ and Ce3+-Gd³⁺-Tb³⁺ co-doped phosphate glass 60P2O5-15CS2O- 15Al2O3-10BaO were studied. The experimental results indicate that, the doping of Ce3+ and Gd³⁺ in Tb³⁺ phosphate glass has a good effect on the 545 nm emission of Tb³⁺ at UV excitation. The Ce3+-Gd³⁺-Tb³⁺ co-doped phosphate glass have a good x-ray luminescence at the radiation of x-ray with energy in 50-120 kev, and a high space resolution. The Ce3+-Gd³⁺-Tb³⁺ co-doped phosphate luminescence glass is a promising material for using in the digital radiography system in medical devices.

不同玻璃组分对掺铒碲酸盐玻璃 光谱性质的影响

Series of tellurite glasses were prepared by traditional melting method, the glass composition were changed and the different effects of glass modifier oxides(alkali metals and alkaline earth metal oxides) and glass intermediate (Y2O3, GeO2, Nb2O5, WO3) on the optical and spectroscopic properties of Er³⁺ doped tellurite glass were researched and compared. The infrared transmitting spectra, absorption spectra and fluorescence spectra were tested, the results showed that Nb2O5 and WO3 in the glass act as part of the body's role in the formation of the network, caused the reduction of transmitting range in infrared wavelength, which decrease the transmitting properties of tellurite glass. The introduction of high valence cationic ions, WO3 especially, can increase the FWHM of Er³⁺ for the increased polarization effect. With the decreasing of cationic field of glass modifier ions, the ion filed of the environment around Er³⁺ increased, subsequently, the role of ligand field polarization effect reduced, which makes the luminescence lifetime increase, and on the contrary the FWHM decrease monotonously.

铕离子掺杂和铕铝共掺高硅氧玻璃的光谱性能

Eu-doped and Eu/Al-codoped high silica glass to investigate the properties of europium ions in high silica glasses were obtained. The porous glasses were immersed into europium nitrate solution or mixed solution of europium nitrate and aluminum nitrate. After dried, the doped porous glasses were sintered at 1200°C to obtain Eu-doped and Eu/Al-codoped high silica glasses. The reduction of Eu³⁺&rarrEu²⁺ was observed in Eu/Al-codoped high silica glass. The ratio of trivalent and bivalent europium ions was adjusted by the addition of aluminum ions and then the luminescent color of the glasses was controlled. A detailed mechanism was given to explain this reduction process.

飞秒激光辐照ZnO晶体

利用飞秒激光对ZnO晶体进行辐照，对辐照前后的晶体样品进行发光光谱及拉曼光谱检测。辐照后发光光谱的某些发光峰强度有明显增强，但未产生新的发光峰，表明没有新的缺陷结构产生，但晶体内锌空位、间隙位锌、间隙位缺陷浓度增加。拉曼光谱结果表明，辐照后ZnO晶体未产生相变，但随着辐照激光功率的增大，拉曼峰327 cm-1，437 cm-1强度明显减弱，表明在飞秒激光辐照作用下氧化锌的结晶程度下降。但574 cm-1峰值却随着辐照功率的增大而变大，分析表明该拉曼峰很可能是由于晶体内间隙位缺陷所致。同时实验过程中观察到飞

Intense frequency upconversion fluorescence of Er3+/Yb3+ co-doped lithium-strontium-lead-bismuth glasses

Infrared-to-visible upconversion fluorescence of Er(3+)/Yb(3+) co-doped lithium-strontium-lead-bismuth (LSPB) glasses for developing potential upconversion lasers has been studied under 975-nm excitation. Based on the results of energy transfer efficiency and upconversion spectra, the optimal Yb(3+)-Er(3+) concentration ratio is found to be 5:1. Intense green and red emissions centered at 525, 546, and 657 nm, corresponding to the transitions 2H_(11/2)-->4I_(15/2), 4S_(3/2)-->4I_(15/2), and 4F_(9/2)-->4I_(15/2), respectively, were observed. The quadratic dependence of the 525-, 546-, and 657-nm emissions on excitation power indicates that a two-photon absorption process occurs under 975-nm excitation. The high-populated 4I_(11/2) level is supposed to serve as the intermediate state responsible for the upconversion processes. The intense upconversion luminescence of Er(3+)/Yb(3+) co-doped LSPB glasses may be a potentially useful material for developing upconversion optical devices.

Structural investigation on TeO2-BiCl3 glassy system

Glass systems of composition xBiCl(3)-(1-x)TeO2 (x=0.2, 0.4, 0.5 and 0.6, respectively) have been investigated by means of DSC, infrared absorption spectroscopy and Raman spectroscopy in order to obtain information about the transformation of structure, thermal and optical properties in the formation of the glass network. The results confirm that the addition of BiCl3 network former increases the glass forming ability and the optical transmission range. And also from Raman results a structural evolution was observed where the number of structural units described as [TeO3] trigonal pyramids, [TeO3+1] polyhedra and ionic behavior bonds (NBO) increases at the expense of the [TeO4] trigonal bipyramids. Bi3+ ions exist in network structure as [BiO6] or [BiCl6] octahedral coordination. As upconversion luminescence glass host, this glassy system is desired for optical properties but the thermal stability will still be improved. (c) 2005 Elsevier B.V. All rights reserved.

Effect of oxygen substitution by halide ions on structure, thermal stability and upconversion fluorescence in Er3(+)/Yb3(+)-codoped germanium-bismuth glasses

For the first time. effect of halide ions (F-, Cl-, Br-, and I-) introduction on structure, thermal stability, and upconversion fluorescence in Er3+/Yb3+-codoped oxide-halide germanium-bismuth glasses has been systematically investigated. The results show that halide ions modified germanium-bismuth glasses have lower maximum phonon energy and phonon density, worse thermal stability. longer measured lifetimes of I-4(l1/2) level, and stronger upconversion emission than germanium-bismuth glass. All these results indicate that halide ions play an important role in the formation of glass network, and have an important influence on the upconversion luminescence. The possible upconversion mechanisms of Er3+ ion are also evaluated. © 2005 Elsevier Ltd. All rights reserved.

Host dependent frequency upconversion of Yb3+/Tm3+-codoped oxyfluoride tellurite glasses

The upconversion luminescence properties of Yb3+/Tm3+-codoped oxyfluoride tellurite glasses under 980 nm excitation are investigated experimentally. The intense blue and relatively weak red emissions centered at 475 and 649 nm corresponding to the transitions (1)G(4) -> H-3(6) and (1)G(4) -> H-3(4) of Tm3+, respectively, are simultaneously observed at room temperature. The effect of PbF2 on upconversion intensity is observed and discussed, and possible upconversion mechanisms are evaluated. The intense blue upconversion luminescence of Yb3+/Tm3+-codoped oxyfluoride tellurite glasses may be a potentially useful material for developing blue upconversion optical devices. (c) 2005 Elsevier B.V. All rights reserved.

Tm3+/Er3+/Yb3+-codoped oxyhalide tellurite glasses as materials for three-dimensional display

Blue, green and red emissions through frequency upconversion and energy transfer processes in Tm3+/Er3+/Yb3+-codoped oxyhalide tellurite glass under 980 nm excitation are investigated. The intense blue (476 nm), green (530 and 545 nm) and red (656 nm) emissions are simultaneously observed at room temperature. The blue (476 nm) emission was originated from the (1)G(4)->H-3(6) transition of Tm3+. The green (530 and 545 nm), and red (656 nm) upconversion luminescences were identified from the H-2(11/2)->I-4(15/2), S-4(3/2)->I-4(15/2), and F-4(9/2)->I-4(15/2) transitions of Er3+, respectively. The energy transfer processes and possible upconversion mechanisms are evaluated. (C) 2005 Elsevier B.V. All rights reserved.

Host dependent thermal stability and frequency upconversion of Er3+-doped heavy metal oxyfluoride germanate glasses

The upconversion properties of Er3+-doped heavy metal oxyfluoride germanate glasses under 975 nm excitation have been investigated. The intense green (551 and 529 nm) and relatively weak red (657 nm) emissions corresponding to the transitions S-4(3/2) -> I-4(15/2), H-2(11/2) -> I-4(15/2) and F-4(9/2) -> I-4(15/2), respectively, were simultaneously observed at room temperature. The content of PbF2 has an important influence on the upconversion luminescence emission. With increasing content of PbF2, the intensities of green (529 nm) and red (657 nm) emissions increase slightly, while the green emission (551 nm) increases markedly. These results suggest that PbF2 has an influence on the green (551 nm) emission more than on the green (529 nm) and red (657 nm) emissions.

Efficient frequency upconversion emission in Er3+-doped novel strontium lead bismuth glass

Er3+ -doped strontium lead bismuth glass for developing upconversion lasers has been fabricated and characterized. The Judd-Ofelt intensity parameters Omega(1) (t = 2,4,6), calculated based on the experimental absorption spectrum and Judd-Ofelt theory, were found to be Omega(2) = 2.95 x 10(-20), Omega(4) = 0-91 X 10(-20), and Omega(6) = 0.36 x 10(-20) cm(2). Under 975 nm excitation, intense green and red emissions centered at 525, 546, and 657 nm, corresponding to the transitions H-2(11/2) --> I-4(15/2), S-4(3/2) I-4(15/2), and F-4(9/2) --> I-4(15/2) respectively were observed. The upconversion mechanisms are discussed based oil the energy matching and quadratic dependence on excitation power, and the dominant mechanisms are excited state absorption and energy transfer upconversion for the green and red emissions. The long-lived I-4(11/2) level is supposed to serve as the intermediate state responsible for the upconversion processes. (C) 2004 Published by Elsevier B.V.

Effect of chloride ions' introduction on structural, thermal stability, and spectroscopic properties in Yb3+Er3+-codoped germanate-bismuth-lead glasses

Yb3+Er3+-codoped chloride-modified germanate-bismuth-lead glasses have been synthesized by the conventional melting and quenching method. Structural and thermal stability properties have been obtained on the basis of the Raman spectra and differential thermal analysis, which indicate that the PbCl2 addition has an important influence on the phonon density of states, maximum phonon energy, and thermal stability of host glasses. The Judd-Ofelt intensity parameters and quantum efficiencies were calculated on the basis of the Judd-Ofelt theory and lifetime measurements. For the 1.53 mu m emission band, the full widths at the half-maximum increase and peak wavelengths are blueshifted with increasing PbCl2 content. Moreover, the effect of the PbCl2 addition on the phonon density of states, OH- content, and upconversion luminescence has been discussed and evaluated. Our results reveal that, with increasing PbCl2 content, the decrease of phonon density and OH- content contributes more to the enhanced upconversion emissions than that of maximum phonon energy. (c) 2005 Optical Society of America

Host dependent frequency upconversion of Er3+-doped oxyfluoride germanate glass

Er3+-doped oxyfluoride germanate glasses have been synthesized by the conventional melting and quenching method. The Judd-Ofelt intensity parameters were calculated based on the Judd-Ofelt theory and absorption spectra measurements. With the substitution of PbF2 for PbO, the Omega(2) parameter decreases, while the Omega(6) parameter increases. These change trends indicate that fluoride anions come to coordinate erbium cations and the covalency of the Er-O bond decreases. Structural and thermal stability properties were obtained by Raman spectra and differential thermal analysis, indicating that PbF2 plays an important role in the formation of glass network and has an important influence on the maximum phonon energy and thermal stability of host glasses. Intense green and red emissions centered at 525, 546, and 657 nm, corresponding to the transitions H-2(11/2) -> I-4(15/2), S-4(3/2) -> I-4(15/2), and F-4(9/2) -> I-4(15/2), respectively, were simultaneously observed at room temperature. With increasing PbF2 content, the intensity of red (657nm) emissions increases significantly, while that of the green (525 and 546nm) emission increases slightly. The results indicate that PbF, has more influence on the red (657nm) emission than the green (525 and 546nm) emissions in oxyfluoride germanate glasses. The possible upconversion luminescence mechanisms have also been estimated and discussed. (c) 2005 Elsevier B.V. All rights reserved.

Intense frequency upconversion fluorescence emission of Er3+/Yb3+-codoped oxychloride germanate glass

Structural and frequency upconversion fluorescence properties of Er3+/Yb3+-codoped oxychloride germanate glasses have been investigated. The Raman spectrum investigation indicates that PbCl2 plays an important role in the formation of glass network and has an important influence on the upconversion luminescence. Intense green and red emissions centered at 525, 546 and 657 nm, corresponding to the transitions H-2(11/2) -> I-4(15/2), S-4(3/2) -> I-4(15/2) and F-4(9/2) -> I-4(15/2), respectively, were observed at room temperature. The possible upconversion mechanism was also estimated and evaluated. Intense upconversion luminescence indicates that Er3+/Yb3+-codoped oxychloride germanate glass is a promising laser material. (c) 2005 Elsevier B.V. All rights reserved.