2 μm mid-infrared optical spectra of Tm3+-doped germanium gallate glasses

Glasses with the composition of 65GeO212Ga2O3-10BaO-8Li2O-5La2O3(molar ratio) doped with 1.526 wt.%, 3.006 wt.%, 5.836 wt.%, 11.028 wt.%, and 15.678 wt.% Tm2O3, respectively, were fabricated by conventional melting method. According to the absorption spectra and the Judd-Ofelt theory, the J-O strength parameters (Ω2,Ω4, Ω6) were calculated, with which the radiative transition probabilities,branching ratios and radiative lifetimes were obtained. The infrared emission spectra (with 808 nm LD excitation) at～1.47 and～1.8 μm of various concentrations of Tm3+-doped glasses were studied. The emission intensity at～1.8 μm reached to the maximum when the Tm2O3-doping concentration was near to be～3.006 wt.% (1.0 mol.%), and then decreased as doping concentration increased further. The mechanism of the fluorescence intensity change was explained with the cross-relaxation effect and the concentration quenching effect of Tm3+. Meanwhile, according to McCumber theory, the absorption and emission cross-sections corresponding to the 3F4→3H6 transitions of Tm3+ at 1.8 μm was obtained. For Tm3+-doped germanate glasses, the maximum emission cross-section reached a value higher than that re-ported for fluorozircoaluminate glasses. It is expected to be a favorable candidate host for～2.0 μm mid-inflated laser because the glass shows favorable optical spectra.

Laser Cooling Using Anti-Stokes Fluorescence in Yb^(3+)-Doped Fluorozirconate Glasses

The fluorozirconate glasses ZBLANP( ZrF\-4-BaF\-2-LaF\-3-AlF\-3-NaF-PbF\-2) doped with different Yb\+ 3+ concentration were prepared. The Raman spectra and absorption spectra are measured to substantiate the existence of phonon-assisted emission. After analyzing the normalized absorption spectra of samples with different Yb\+ 3+-doped concentration, we calculated the maximum cooling effect in the 3 wt% Yb\+ 3+-doped sample pumped at 1 012.5 nm. The corresponding cooling capability is about -4.09 ℃/W and the cooling efficiency reaches 1.76%.

Spectral and Lasing Properties of Er^(3+0/Yb^(3+) Co-Doped Phosphate Glasses Pumped by LD

Er^3 ＋/Yb^3 ＋ phosphate glasses were fabricated. According to McCumber theory, the stimulated emission cross-section of Er^3＋ ions at 1533 nm was calculated on the basis of absorption spectrum, and 0.84 × 10^-20 cm^2 is derived, the fluorescence lifetime of ^4I13/2 level is 8.5 ms. An Er^3＋/Yb^3＋ co-doped phosphate glass CW laser pumped by LD was demonstrated at room temperature. The maximum output power is 80 mW and slope efficiency is 16.5%.

Optical Spectroscopy of Er^(3+) and Er^(3+)/Yb^(3+)Co-doped Bi_2O_3-GeO_2-B_2O_3-ZnO Glasses

The （60 - x）Bi2O3 - xGeO2-30B2O3-10ZnO （x = 5, 10, 20, 30 molar percent） glasses doped with Er^3＋ and Er^3＋/Yb^3＋ were fabricated using the melting method. The thermal stability of the glasses was studied with their DTA curves. The results show that the difference between the glass transition temperature and the crystallization onset temperature increases with the increase of GeO2 content, indicating that the thermal stability of the glass has become better. The absorption spectra were recorded and the stimulated emission cross sections were calculated using the McCumber theory. The Ω2, O4, and Ω6 parameters,the transition probability, the radiative lifetime, and the fluorescence branch ratio of Er^3＋ for optical transition were calculated from their absorption spectra in terms of reduced matrix U^（t）（λ = 2, 4, 6） character for optical transitions. The infrared emission of Er^3＋ was measured upon excitation with 970 nm light and the full width at half-maximum （FWHM） was estimated from the emission spectra. The pumping efficiency and the intensity of the emission at the 1.54 μm band of Er^3＋ were enhanced considerably by co-doping Yb^3＋ .

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.

Preparation and Optical Properties of Er^(3+)-Doped Gadolinium Borosilicate Glasses

Er^(3+)-doped Gd_2O_3 -SiO_2 -B_2O_3 -Na_2O glasses were prepared, and formation range of glass of Gd_2O_3 -SiO_2 -B_2O_3 system was experimentally obtained. It is found that the glass phase can be formed only when the content of SiO_2 is 0～50%(molar fraction), Gd_2O_3 is 0～30%(molar fraction) and B_2O_3 is above 20%(molar fraction) in this glass system. The glass can also be obtained but becomes translucent at the contents of 60%(molar fraction) SiO_2 and 30% Gd_2O_3 , or at the contents of 60%(molar fraction) SiO_2 and 30%(molar fraction) B_2O_3. There is no glass phase formed in other glass components. Glass forming ability for Gd_2O_3 content of 10%, was characterized by the value of β, the parameter of crystallization tendency, which is 0.32～1.76, obtained from the differential thermal analysis. The absorption and emission cross section, the J-O parameters Ωt_((2,4,6)) and radiative transition probabilities were calculated by using the theory of McCumber and Judd-Ofelt. The emission properties at 1.5 μm of the samples are discussed with the product of full width at half maximum and stimulated emission cross section. It can be seen that the value of the FWHM×σ_e^(peak) product in the prepared glass is more than those of germanate, silicate and phosphate glasses. Furthermore, the maximum value of the product among these glasses reported in this work is close to that of oxyfluoride silicate glass. Therefore, the Er^(3+)-doped gadolinium borosilicate glass in this paper is a candidate for broadband erbium doped fiber amplifiers.

Frequency Up-conversion Luminescence Properties and Mechanism of Tm^(3+) /Er^(3+)/Yb^(3+) Co-doped Oxyfluorogermanate Glasses

Oxyfluoride glasses were developed with composition 60GeO 2 ·10AlF 3 ·25BaF 2 ·（1.95-x）GdF 3 · 3YbF 3 ·0.05TmF 3 ·xErF 3 （x=0.02,0.05,0.08,0.11,0.14,0.17）in mole percent.Intense blue（476 nm）,green（524 and 546 nm）and red（658 nm）emissions which identified from the 1G 4 →3H 6 transition of Tm3＋and the（2H 11/2 ,4S 3/2 ）→4I 15/2 ,4F 9/2 →4I 15/2 transitions of Er3＋,respectively,were simultaneously observed under 980 nm excitation at room temperature.The results show that multicolor luminescence including white light can be adjustably tuned by changing doping concentrations of Er3＋ion or the excitation power.In addition,the energy transfer processes among Tm3＋,Er3＋and Yb3＋ions,and up-conversion mechanisms are discussed.

Spectroscopic Properties of Er^(3+)-Doped TeO_2-WO_3-ZnO-ZnF_2 Glasses

The Er^(3+)-doped TeO_2-WO_3-ZnO-ZnF_2(TWZOF) glasses were prepared. The absorption spectra, 1.5 μm emission spectra and fluorescence lifetimes of Er^(3+), excited at 970 nm, were measured. The J-O parameters Ω_ t (t =2, 4, 6), absorption and emission cross-sections were calculated. The dependence of the 1.5 μm emission intensity, fluorescence lifetime and bandwidth of the Er^(3+) emission upon the contents of ZnF_2 in glass were investigated. In TWZOF glass, Er^(3+) ions had a broad emission profile around 1.5 μm with the maximum FWHM of 83 nm. With the increasing of the content of ZnF_2, the emission intensity at peak wavelength and the fluorescence lifetime of Er^(3+) at 1.5 μm increase.

Spectroscopic Properties of Nd^(3+)-Doped Tellurite Glasses

The Nd^3＋-doped pared. The absorption and tellurite glasses were preemission spectra of Nd^3 ＋- doped tellurite glasses at room temperature were measured. The Judd-Ofelt parameters （Ω2, Ω4, Ω6） of the glasses were calculated from measured absorption spectra. The calculation results of luminescence properties （A, β, τrad, σ） of Nd^3＋ ions in the tellurite were glasses were given. Spectroscopic properties, concentration quenching in these kinds of the glasses were investigated. The results indicate that the tellurite glasses with composition of 70% TeO2, 20% ZnO, （ 10 - x ） % La2O3, x % Nd2O3 （ mol% ） show high emission cross section and low phonon energy. The fluorescent intensity and the emission cross section have a maxi- mum value at x = 0.5, namely, the optimum Nd^3 ＋ ion concentration in the tellurite glass is 0.5% （1.93 × 10^20 ions·cm^-3）. The fluorescence properties of Nd^3＋ measured are basically in accord with the calculated results.

Optical Spectroscopy of Er^(3+), Er^(3+)/Yb^(3+) Co-doped Bi_2O_3-GeO_2-B_2O_3-ZnO Glasses

The （60 - x） Bi2O3-xGeO2-30B2O3-10ZnO （x = 5, 10, 20, 30 molar percent） glasses doped with Er^3＋ and Er^3＋/Yb^3＋ were fabricated by melting method. The thermal stability of the glasses was studied by their DTA curves. The results indicate that the difference between the glass transition temperature and the crystallization onset temperature increase as increase of GeO2 content, indicating that the thermal stability of the glass becomes better. The absorption spectra were recorded. The stimulated emission cross sections were calculated by McCumber theory. The Ω2, Ω4, and Ω6 parameters, transition probability, radiative lifetime, fluorescence branch ratio of Er^3＋ for optical transition were calculated from their absorption spectra in terms of reduced matrix U^（1）（λ = 2, 4, 6） character for optical transitions. The infrared emission was measured by excitation with 970 nm light and the FWHM was estimated from their emission spectra. The pumping efficiency and the intensity of emission at the band of 1.54 μm are enhanced greatly by addition of Y2O3.

Up-conversion photoluminescence characteristics of Yb^(3+):Er^(3+):Tm^(3+) co-doped borosilicate glasses

Yb^3＋：Er^3＋：Tm^3＋co-doped borosilicate glasses are prepared. Their strong up-conversion photoluminescence spectra in a range from ultra-violet to near-infrared, which are excited by a 978-nm laser diode, are measured, and the mechanisms of energy transfer among Yb^3＋ Er^3＋ and Tm^3＋ ions are discussed. The results show that there is an unexpected wavelength at 900-nm emission from Yb^3＋ Stark splitting levels to pump Tm^3＋ ions and there exists an optimum pump power. The concentration of the Tm^3＋ dopant gives rise to a prominent effect on the intensity of visible and near-infrared emissions for the yb^3＋：Er^3＋：Tm^3＋ co-doped borosilicate glasses.

The influence of cation additives on the NIR luminescence intensity of Er^(3+)-doped borate glasses

Er3+-doped 25BaO-(25-x)SiO2-xAl2O3-25B2O3 transparent glasses are prepared with x = 0,12.5 and 25 by a solid-state reaction.The Er-related NIR luminescence intensity,which corresponds to the transition of 4I15/2-4I13/2,is obviously altered with different silicon/aluminum ratios.The Judd-Ofelt parameters of the Er3+ ions are adopted to explain the intensity change in the NIR fluorescence,and the Raman scattering intensity versus the amount of Al and/or Si components are discussed.The spectra of the three samples are quite similar in the peak positions,but different in intensity.The maximal phonon density of state for the samples is calculated from the Raman spectra and is correlated to the NIR luminescence efficiency.

Green and red up-conversion emissions and thermometric application of Er^(3+) -doped silicate glass

The green and red up-conversion emissions centred at about 534, 549 and 663 nm of wavelength, corresponding respectively to the ^2H11/2 → ^4I15/2, ^4S3/2 → ^4I15/2 and ^4F9/2 → ^4I15/2 transitions of Er^3＋ ions, have been observed for the Er^3＋-doped silicate glass excited by a 978 nm semiconductor laser beam. Excitation power dependent behaviour of the up-conversion emission intensity indicates that a two-photon absorption up-conversion process is responsible for the green and red up-conversion emissions. The temperature dependence of the green up-conversion emissions is also studied in a temperature range of 296-673 K, which shows that Er^3＋-doped silicate glass can be used as a sensor in high-temperature measurement.

Three-photon-excited fluorescence of Tb^(3+)-doped CaO-Al_2O_3-SiO_2 glass by femtosecond laser irradiation

A near infrared to visible blue, green, and red upconversion luminescence in a Tb^3＋-doped CaO-Al2O3-SiO2 glass was studied, which was excited using 800 nm femtosecond laser irradiation. The upconversion luminescence was attributed to ^5D3→^7F5, ^5D3→^7F4, ^5D3→^7F3, ^5D4→^7F6, ^5D4→^7F5, ^5D4→^7F4, and ^5D4→^7F3 transitions of Tb^3＋. The relationship between upconversion luminescence intensity and the pump power indicated that a three-photon simultaneous absorption process was dominant in this upconversion luminescence. The intense red, green, and blue upconversion luminescence of Tb^3＋-doped CaO-Al2O3-SiO2 glass may be potentially useful in developing three-dimensional display applications.

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.

Investigation on Preparation and Fluorescence Properties of Oxy-Fluoride Glass Co-Doped with Er^(3+) and Yb^(3+)

The glass sample based on the composition of 45PbF_2-45GeO_2-10WO_3 co-doped with Yb^(3+)/Er^(3+) was prepared by the fusion method in two steps: melted at 950 ℃ for 20～25 min then annealed at 380 ℃ for 4 h. Through the V-prism it is found that the refractive index of host glass and the sample are 1.517 and 1.65 respectively. The transmittance was observed by using the ultraviolet-visible-infrared spectrometer in the wavelength range from 0.35 to 2.5μm. The transmittance of the host glass is beyond 73%. That of the sample is beyond 50% and there are characteristic absorption peaks of rare-earth ions. The emission spectrum was measured by using the Hitachi F-4500 fluorescent spectrometer pumped by 980 nm semiconductor laser. There are a strong emission peak at 530 nm and a weak peak at 650 nm.

Optical temperature sensor based on up-conversion fluorescence emission in Yb^(3+):Er^(3+) co-doped ceramics glass

yb^3＋：Er^3＋ co-doped oxy-fluoride ceramics glass has been prepared. The mechanism of up-conversion emissions about Er^3＋ was discussed, and the temperature properties of green up-conversion fluorescence between 303 and 823 K were investigated. The results show that the sensitivity of this sample reaches its maximum value, about 0.0047 K^-1, when the temperature is 383 K, indicating that this kind of sample can be used as high temperature and high sensitivity optical temperature sensor.

Tm^(3+)-doped tellurite glass with Yb^(3+) energy sensitized for broadband amplifier at 1400–1700 nm bands

A kind of novel experiment was disclosed as it possessed two bands of fluorescence emission at 1.4 and 1.6 μm, which were perfectly complimentary to the current C band of optic communication. The fluorescence was based on energy transfer and up-conversion processes between Tm^3＋ and Yb^3＋ under direct pumping of 975 nm LD. The spectra and lifetimes of Tm^3＋ fluorescence in the tellurite glass were described. The corresponding fluorescence characteristics and energy migration process were analyzed by the method of lifetime and intensity comparison. The mechanism of the up-conversion based IR fluorescence was presented upon analyzing the multi-photon pumping process. The potential advantages of Tm^3＋/Yb^3＋ co-doped tellurite glass as amplifier material were concluded.

High Quantum Efficiency and High Concentration Erbium-Doped Silica Glasses Fabricated by Sintering Nanoporous Glasses

A new method was used to prepare erbium-doped high silica （SiO2 % 〉 96 % ） glasses by sintering nanoporous glasses. The concentration of erbium ions in high silica glasses can be considerably more than that in silica glasses prepared by using conventional methods. The fluorescence of 1532 nm has an FWHM （Full Wave at Half Maximum） of 50 nm, wider than 35 nm of EDSFA （erbium-doped silica fiber amplifer）, and hence the glass possesses potential application in broadband fiber amplifiers. The Judd-Ofelt theoretical analysis reflects that the quantum efficiency of this erbium-doped glass is about 0.78, although the erbium concentration in this glass （6 × 10^3） is about twenty times higher than that in silica glass. These excellent characteristics of Er-doped high silica glass will be conducive to its usage in optical amplifiers and microchip lasers.

Investigation of Silver Nanostructures and Their Influence on the Fluorescence Spectrum of Erbium-Doped Glasses

Sodium borate glasses embedded with silver were made by the melt quenching technique. Glass transition temperature was recorded by thermal analysis of the sample. As made glasses revealed emission in the visible region under nitrogen laser and excimer laser excitations. Heat treatment was used to induce silver metallic particles. Absorption spectra revealed a peak at 417 nm due to surface Plasmon resonance. Particle size was estimated to be 2.6 ± 0.2 nm. Erbium and silver co-doped multielement oxide glasses were made by the melt quenching technique followed by heat treatment to induce nanoparticles. In heat treated samples, Er3+ luminescence increased 4× due to enhanced field in the vicinity of silver particles. Under excimer laser excitation, Er3+ and 2% Ag co-doped glass revealed Er3+ transitions due to enhanced field at the rare-earth ions. Under 795 nm laser excitation Er3+ green upconversion signals are found to be 4× stronger in 2% Ag co-doped, heat treated sample, than the others.