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.     

Upconversion Luminescence Dynamics in Er^3＋/Yb^3＋ Codoped Nanocrystalline Yttria

The upconversion luminescence and dynamics in Er^3＋ /Yb^3＋ codoped nanocrystalline yttria （7-65 nm） are studied under 980-nm pulsed laser excitation, It is found that the red emission of ^4F9/2-^4I15/2 and the green emission of ^2H11/2/^4S3/2 in nanoparticles with lower concentration of Yb^3＋ result from a two-photon excitation, In nanocrystals with higher Yb^3＋ concentration, the red emissions from a two-photon excitation, while the green emissions from a three-photon excitation, The luminescence dynamics indicates that as the particle size decreases, both the rise and the decay time constants become shorter, As the size decreases to several nanometres, the rise process nearly disappears, suggesting that the upconversion luminescence originates mainly from self-excitation of Er^3＋, instead of the energy transfer of Yb^3＋→ Er^3＋.     

Mechanisms and Concentration Dependence of Upconversion Fluorescence in Er^3＋ and Tm^3＋ Codoped Tellurite Glasses

We investigate the upconversion luminescence of Er3^ and Tm^3 codoped tellurite glasses under both the 975 and 80Ohm excitations. By Tm^3 codoping, the Er^3 green emission corresponding to the (^4S3/2, 2H11/2) → 4I15/2 transitions was quenched, while the red emission corresponding to the ^4F9/2 → ^4I15/2 transition was selectively sensitized. The red emission has a maximum in the range where the ratio of Er^3 - to Tm^3 -content is about two and its fluorescence intensity becomes 1.5 and 5 times larger at the maximum than those in the absence of Tm^3 for 975 and 800 nm excitations, respectively. The results were explained considering the influence of energy transfers between these two active ions.     

Laser-diode excited intense upconversion luminescence of Er^3＋ in bismuth-lead-germanate glasses

We have investigated infrared-to-visible upconversion luminescence of Er^3＋ in bismuth-lead-germanate glasses. The UV cutoff wavelength is shortened while its lifetime is increased almost linearly, with PbF2 substituting for PbO in the bismuth-lead germanate glasses. Three emissions centred at around 529, 545 and 657 nm are clearly observed, which are identified as originating from the ^2H11/2→^4 I15/2,^4S3/2→^4 I15/2 and ^4 F9/2 →^4 I15/2 transitions, respectively. It is noted that all the upconversion emission intensities increase with PbF2 concentration increasing. The ratio between the intensities of red and green emissions increases with the increasing of PbF2 content. Energy transfer processes and nonradiative phonon-assisted decays account for the populations of the ^2 H11/2,^4 S3/2 and ^4F 9/2 levels. The quadratic dependence of fluorescence on excitation laser power confirms a two-photon process to contribute to the upconversion emissions.     

2-um emission performance of Tm^3＋-Ho^3＋ co-doped tellurite glasses

The emission properties of 2-um region fluorescence of Tm^3＋-Ho^3＋ co-doped tellurite glasses are investigated. Introducing F- ions to the composition of tellurite glasses plays a positive effect on the 2-#m emission. A maximum intensity of 2-um emission is achieved when 1.5-mol% Tm2O3 and 1-mol% Ho203 concentration are doped in the glasses. The emission cross section and gain coefficient of the ^5I8-^5I7 transition of Ho^3＋ are calculated. The emission cross section has a maximum of 1.29×10-20 cm^2 at 2048 nm wavelength. The results indicate that Tm＆3＋-Ho^3＋ co-doped tellurite glasses are suitable for 2-um application.     

Upconversion luminescence of Tm^3＋/Yb^3＋ codoped oxyfluoride glasses

Novel oxyfluoride glasses are developed with the composition of 30SiO2-15Al2O3-28PbF2-22CdF2-0.1TmF3 - xYbF3 - （4.9 - x） AlF3（x=0, 0.5, 1.0, 1.5, 2.0） in tool fraction, Furthermore, the upconversion luminescence characteristics under a 970nm excitation are investigated. Intense blue, red and near infrared luminescences peaked at 453nm, 476nm, 647nm and 789nm, which correspond to the transitions of Tm^3＋： ^1D2 →^3F4, ^1G4 →^3H6, ^1G4 →^3F4, and ^3H4 →^3H6, respectively, are observed. Due to the sensitization of Yb^3＋ ions, all the upconversion luminescence intensities are enhanced considerably with Yb^3＋ concentration increasing. The upconversion mechanisms are discussed based on the energy matching rule and quadratic dependence on excitation power. The results indicate that the dominant mechanism is the excited state absorption for those upconversion emissions.     

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.     

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.     

Frequency Upconversion Emission of Er^3＋-Doped Strontium-Lead-Bismuth Glasses

Er^3 -doped strontium-lead-bismuth glasses for developing potential upconversion lasers have been fabricated and characterized. Under 975 nm excitation, intense green and red emissions centred at 525, 546, and 657nm,corresponding to the transitions ^2H11/2 → ^4I15/2, ^4S3/2 → ^4I15/2, and ^4F9/2 → ^4I15/2, respectively, were observed at room temperature. The upconversion mechanisms are discussed based on the energy matching and quadratic dependence on excitation power, and the dominant mechanisms are excited state absorption and energy transfer upconversion for 525 and 546nm emissions, and energy transfer upconversion for 657nm emission.     

Energy transfer mechanism in Er3＋ doped fluoride glass sensitized by Tm3＋ or no3＋ for 2.7-μm emission

Enhanced 2.7 μm emission is obtained in Er3＋/Tma＋ and Era＋/Ho3＋ codoped ZBYA glasses. Absorp- tion and emission spectra are tested to characterize the 2.7 μm emission properties of Era＋/Tm3＋ and Era＋/Ho3＋ doped ZBYA glasses and a reasonable energy transfer mechanism of 2.7 μm emission between Er3＋ and Tm3＋Ho3＋） ion is proposed. Codoping of Tm3＋ or Ho3＋ significantly reduces the lifetime of the Era＋： 4I13/2 level due to the energy transfer of Er3＋：4I13/2 →Tm3＋：3F4 or Er3＋：4I13/2 →Ho3＋： 5I7. Thus, the 2.7μm emission is strengthened and the 1,5μm emission is decreased accordingly especially in the Era＋/Tma＋ sample. The upconversion effects between the Er3＋/Tm3＋ and Er3＋/Ho3＋ doped ZBYA glasses are different attribute to the different energy transfer efficiencies. Both of the two codoped samples possess nearly equal large emission cross section （16.6 × 10 -21 cm-2） around 2.7 μm. The results indicate that this Er3＋/Tm3＋ or Er3＋/Ho3＋ doped ZBYA glass has potential applications in 2.7 μm laser.     

Investigation on Nonradiative Decay of the Er^3＋^4I13/2 → ^4I15/2 Transition in Different Tellurite Glass Matrix

Three kinds of Er^3＋-doped tellurite glasses with different hydroxyl groups are prepared by the conventional melt-quenching method. Infrared spectra are measured to estimate the exact content of OH^- groups in samples. The maximum phonon energy in glasses are obtained by measuring the Raman scattering spectra. The strength parameters Ωt （t = 2, 4, 6） for all the samples are calculated and compared. The nonradiative decay rate of the Er^3＋ ^4I13/2 → ^4I15/2 transition are calculated for the glass samples with different phonon energy and OH^- group contents. Finally, the effect of OH^- groups on fluorescence decay rate of Er^3＋ is analysed, the constant KOH-Er of TWN, TZPL and TZL glasses are calculated to be 9.2 × 10^-19 cm^4s^-1, 5.9 × 10^-19 cm^4s^-1, and 3.5 × 10^-19 cm^4s^-1, respectively.     

Blue Upconversion Luminescence in Tm^3＋／Yb^3＋-Codoped Lead Chloride Tellurite Glass

The upconversion properties of Tm^3 /Yb3 -codoped lead chloride tellurite glass under 980hm excitation were investigated. The intense blue (476nm) emission and weak red (649 nm) emission corresponding to the ^1G4→4 ^3H6 and ^1G4→^3H4 transitions of Tm^3 ions, respectively, were simultaneously observed at room temperature. The dependence of upconversion intensities on excitation power and the possible upconversion mechanisms are evaluated. The intense blue upconversion luminescence of Tm^3 /Yb^3 -codoped lead chloride tellurite glass can be used as potential host material for the development of blue upconversion optical devices.     

Optical parameters and energy levels splitting of Ho^3＋ in Ho^3＋： GdVO4

Ho^3＋ ： GdVO4 is a new laser material suitable for high-power laser systems. In this paper we measure the absorption spectra of Ho^3＋ in the sample Ho^3＋： GdVO4. The intensity parameters are calculated by using the Judd-Ofelt theory. Some predicted spectroscopic parameters, such as the spontaneous radiative transition rate, branching ratio and integrated emission cross section are dealt with. And we also compare the optical parameters with those of other materials. From these results, it is found that there are many transitions which have large oscillator strengths and large integrated emission cross sections. Especially the transitions such as ^5 F4 → ^5 I 8, ^5 S2→^5 I8, ^5 F5 → ^5 I8 and ^5 I7 →^ 5 I8 are useful in solid-state lasers and other fields. Finally, we discuss the splitting of the energy levels of Ho^3＋ in the crystal GdVO4 based on the group theory.     

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.     

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.     

Host dependent thermal stability and frequency upconversion of Er^3＋-doped heavy metal oxyfluoride germanate glasses

The upconversion properties of Er^3＋-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 ^4S3/2→^4I15/2, ^2H11/2→^4 I15/2 and ^4F9/2 →^4I15/2, 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.     

Effects of Yb^3＋ in Er^3＋/Yb^3＋ Codoped Fluorophosphate Glasses

For the Er^3＋ /Yb^3＋ codoped fluorophosphate glasses, Judd-Ofelt theory is used to analyse the influence of YbF3 as not a sensitizer but an average component on the spectroscopic properties around 1530nm emission. The double roles of Yb^3＋, as a sensitizer and as an average component, are discussed. It is found that Yb^3＋ as an average component contributes to the increase of fluorescence lifetime, and Yb^3＋ as a sensitizer has the best sensitization when its concentration is 2.4 mol%.     

Structural and Upconversion Fluorescence Properties of Er^3＋／Yb^3＋-Codoped Lead-Free Germanium-Bismuth Glass

We study the structural and infrared-to-visible upconversion fluorescence properties of Er^3 /yb^3 -codoped leadfree germanium-bismuth glass. The structure of lead-free germanium-bismuth-lanthanum glass is investigated by peak-deconvolution of F~aman spectroscopy. Intense green and red emissions centred at 525, 546, and 657nm,corresponding to the transitions ^2H11/2 → 4I15/2, ^4S3/2 → 4I15/2, and 4F9/2 → 4I15/2, respectively, are observed at room temperature. The quadratic dependence of the 525, 546, and 657nm emissions on excitation power indicates that a two-photon absorption process occurs under 975nm excitation.     

UV-Blue Upconverted Emission from Nd^3＋-Doped InF3-Based Heavy-Metal Fluoride Glasses for Blue Upconversion Fibre Laser

We report spectral properties and thermal stability of Nd^3 -doped InF3-based heavy-metal fluoride glasses. Fluoroindate glasses in the chemical compositions (in mol％) of (38-x)InF3-16BaF2-20ZnF2-20SrF2-3GdF3-1GaF3-2NaF-xNdF3 (x = 0.1, 0.5, 1, 2, 3) have been prepared under a controlled atmosphere in a dry box. Strong UVblue upconversion emission from a green excitation wavelength has been observed and the involved mechanisms have been explained. Near-infrared emission occurs simultaneously upon excitation of the UV-blue upconversion emissions with a cw Ar^ laser. The upconversion spectra have revealed four dominant emissions at 354, 380, 412 and 449nm, which belong to the transitions of ^4D3/2 → ^4I9/2, 4^D3/2 → ^4I11/2 and ^2P3/2 → ^4I9/2, ^4D3/2 → ^4I13/2 and ^2P3/2 → ^4I11/2, ^4D3/2 → ^4I15/2 and ^2P3/2 → ^4I13/2, respectively.     

Frequency Upconversion Fluorescence Emission of Er^3＋-Doped Oxychloride Germanate Glass

Frequency upconversion fluorescence property of Er^3 -doped oxychloride germanate glass is investigated. Intense green and red emissions centred at 525, 546, and 657nm, corresponding to the transitions ^2H11/2→4I15/2,^4S3/2→^4I15/2, and ^4F9/2→^4I15/2, respectively, were simultaneously observed at room temperature. The quadratic dependence of the 525, 546, and 657nm emissions on excitation power indicates that a two-photon absorption process occurs under 975 nm laser diode (LD) excitation. The Raman spectrum investigation indicates that oxychloride germanate glass has the maximum phonon energy at-805cm^-1. The thermal stability of this oxychloride germanate glass is evaluated by differential scanning calorimetry, and thermal stability factor AT(△T = Tx -Tg) is 187℃. Intense upconversion luminescence and good thermal stability indicate that Er^3 -doped oxychloride germanate glass is a promising upconversion laser material.