Nanocrystals precipitation and up-conversion luminescence in Yb~(3 )-Tm~(3 ) co-doped oxyfluoride glasses

Rare earth ions doped oxyfluoride glass with composition of 28SiO2·22AlO1.5·40PbF2·10PbO·(4.8–x) GdF3·0.1NdF3·xYbF3·0.1TmF3 (x=0, 0.1, 0.2, 0.5, 1, 2, 3, 4 and 4.8) in molar ratio was developed. When the oxyfluoride glasses were heat-treated at the first crystallization temperature, the glasses gave transparent glass-ceramics in which rare earth containing fluorite-type nanocrystals of about 17.2 nm in diame-ter uniformly precipitated in the glass matrix. Compared with the glasses before heat treatment, the glass-ceramics exhibited very strong blue up-conversion luminescence under 800 nm light excitation. Rare earth containing nanocrystals were also space selectively precipitated upon laser irradiation in an oxyfluoride glass, the size of precipitated nanocrystals could be controlled by laser power and scan speed. The intensity of the blue up-conversion luminescence was strongly dependent on the precipitation of β-PbF2 nanocrystal and the YbF3 concentration. The reasons for the highly efficient Tm3 up-conversion luminescence after laser irradiation were discussed.     

Preparation and Luminescence of Er^3＋ Doped Oxyfluoride Glass Ceramics Containing LaF3 Nanocrystals

Er^3＋ doped transparent oxyfluoride glass ceramics version and near infrared luminescence behavior of Er^3＋ in containing LaF3 nanocrystals were prepared and the up-conglasses heat-treating time and temperature, the size （varied from 0 to 19 and glass ceramics were investigated. With increasing nm） and crystallinity （varied from 0 to 47%） of LaF3 nanocrystals in the glass ceramics are increased. The up-conversion luminescence intensity of Er^3＋ ions in the glass ceramics is much stronger than that in the glasses The near infrared emission of Er^3＋ ions in and increased significantly with increasing heat-treating time and temperature the glass ceramics is found to be similar to that in the glasses.     

Intense upconversion luminescence of Er3+/Yb3+ codoped oxyfluoride borosilicate glass ceramics containing Ba2GdF7 nanocrystals

Er3+/Yb3+-codoped transparent oxyfluoride borosilicate glass ceramics containing Ba2GdF7 nanocrystals were prepared and spectroscopic properties of rare earth ions were investigated.Fluoride nanocrystals Ba2GdF7 were successfully precipitated in glass matrix,which was confirmed by X-ray diffraction(XRD)and transmission electron microscopy(TEM)results.In comparison with the as-made precursor,significant enhancement ofupconversion luminescence was observed in the Er3+/Yb3+codoped oxyfluoride glass ceramics,which may be due to the variation of coordination environment around Er3+and Yb3+ions after crystallization.The transition mechanisms of the green and red upconversion luminescence were ascribed to a two-photon process,and that of the blue upconversion luminescence was a three-photon process.     

Up-conversion of Er3＋/yb3＋ co-doped transparent glass-ceramics containing Ba2LaF7 nanocrystals

The up-conversion of Er3+/Yb3+co-doped transparent glass-ceramics 50SiO2-10AlF3-5TiO2-30BaF2-4LaF3-0.5ErF3-0.5YbF3 containing Ba2 LaF7 nanocrystals under the changing of heat treatment temperature and time were investigated.The Ba2 LaF7 nanocrystals precipitated from the glass matrix was confirmed by X-ray diffraction(XRD).The structural investigation carried out by XRD and transmission electron microscopy(TEM) evidenced the formation of cubic Ba2 LaF7 nanocrystals with crystal size of about 14 nm.Comparing with the samples before heat treatment,the high efficiency up-conversion emission of Er3+/Yb3+co-doped samples was observed in the glass-ceramics under 980 nm laser diode excitation.The increase in red emission intensity bands was stronger than the green bands when the crystal size increased.The mechanism for the up-conversion process in the glass-ceramics and the reasons for the increase of Er3+/Yb3+co-doped up-conversion intensity after heat treatment were discussed.     

Luminescence of Er^3＋ in Oxyfluoride Transparent Glass-Ceramics

Erbium doped silicate, germanate, and tellurium-germanate oxyfluoride glasses were prepared in a bulk form. Through appropriate heat treatment of the as-prepared glasses, transparent glass-ceramics (TGCs) were obtained with the formation of β-PbF2∶Er3 nanocrystals in the glass matrix were confirmed by X-ray diffraction. Well-defined diffraction peaks were observed in the samples after heat-treatment. The average crystal diameter of these precipitated crystals from full-width at half-maximum (FWHM) of the diffraction peak was estimated to be between 8 and 13 nm. Optical absorption, photoluminescence, and upconversion luminescence were measured on as-prepared glass and glass-ceramics. Luminescence spectra in the TGC samples revealed well-resolved, sharp stark-splitting peaks, which indicates that a majority of Er3 ions has been incorporated into the crystalline phase of the nanocrystals. The intensity of the visible and near infrared luminescence mostly increases in TSG compared to that in the as-prepared glass. In 1.53 μm absorption and emission bands, the maximum absorption peak is blue-shifted from 1531 to 1507 nm, whereas the maximum emission peak is red-shifted from 1535 to 1543 nm in TGC, as compared with that in glass. The bandwidth at half-maximum (BWHM) of the emission band is significantly broader in TGC than in glass, which is beneficial to the erbium-doped fiber amplifier (EDFA). Upconversion luminescence was measured using 800 nm near-infrared light excitation. Drastically increased upconversion luminescence was observed from the TGC as compared to that from their corresponding as-prepared glasses. In addition to a strong green emission centered at 545 nm because of 4S3/2→4I15/2 transition and a weaker red emission centered at 662 nm because of 4F9/2→4I15/2 transition, generally seen from the Er3 doped glasses, two violet emissions centered at 410 nm because of 2H9/2→4I15/2 transition and centered at 379 nm because of 4G11/2→4I15/2 transition were also observed from the TGC. The increased luminescence was attributed to the decreased effective phonon energy and the increased energy transfer between the excited ions when Er3 ions were incorporated into the precipitated β-PbF2 nanocrystals. The results indicated two attractive spectroscopic properties of the Er3 doped TGC samples, compared to glass samples, namely a reduced multiphonon decay rate and a reduced inhomogeneous broadening. In addition, these oxyfluoride TGC materials were robust, easy and flexibile to process, and possible to be fabricated in the fiber form for device applications.     

Spectroscopic investigations on Er3+/Yb3+-doped oxyfluoride glass ceramics containing YOF nanocrystals

Spectroscopic properties of Er3+/Yb3+-doped transparent oxyfluoride borosilicate glass ceramics containing YOF nanocrystals were systematically investigated. X-ray diffraction (XRD) confirmed the formation of YOF nanocrystals in the glassy matrix. Based on the Judd-Ofelt theory, the intensity parameters Ωi (i=2, 4, 6), spontaneous emission probability, radiative lifetime, radiative quantum efficiency and the effective emission bandwidth were investigated. The upconversion luminescence intensity of Er3+ ions in the glass ceramics increased significantly with the increasing crystallization temperature. The transition mechanisms of the green and red upconversion luminescence were ascribed to a two-photon process, and the blue upconversion luminescence was a three-photon absorption process.     

Preparation and luminescence properties of Ce3＋/Dy3＋-codoped fluorosilicate glass ceramics

The Ce3+and Dy3+ co-doped fluorosilicate glass and glass ceramics containing SrF2 or CeF3 nanocrystals were prepared under re-ducing atmosphere. The precipitated nano-crystalline phase shifted from cubic SrF2 to hexagonal CeF3 gradually with the heat treatment tem-perature increasing from 620 to 680 °C. The glass and glass ceramics emitted white light, deriving from a combination of the Ce3+ blue and the Dy3+ yellow light. The CIE coordinates could be tuned by adjusting the ratio of Ce3+/Dy3+ concentration. The luminescence could be en-hanced significantly by annealing the samples at the temperatures lower than 640 °C.     

A blue luminescence glass-ceramics of Eu^2＋ ions activated Li2O-BaO-B2O3

New blue luminescence glass-ceramic samples were prepared in air by annealing of the Eu^3＋-doped Li2O-BaO-B2O3 glass. The as-made glass samples only showed the sharp emission peaks assigned to the transitions of 5^D0-7^Fj （J=0, 1, 2, 3, 4） of Eu^3＋ ions. The glass-ceramic samples gave a strong and broad emission band peaking at about 382 nm ascribed to the 5d-4f transition of Eu^2＋ ions. The optical properties such as excitation and emission spectra, and the decay time of the Eu^2＋ ions were investigated in the glasses or the glass-ceramics samples. The X-ray diffraction pattern showed that LiBan9O15 might be demonstrated to be the crystallites in the glass-ceramic, which contributed to the blue luminescence. SEM micrograph was investigated on the glass-ceramic samples obtained by crystallization of the glass matrix resulting in a mixture of poly-crystals.     

Local vibration around rare earth ions in alkaline earth fluorosilicate transparent glass and glass ceramics using Eu~(3 ) probe

By heat treating the alkaline earth fluorosilicate glass, transparent glass ceramics containing alkaline earth fluoride nanocrystallites were prepared. The luminescence spectra and phonon sideband associated with the Eu3 :5D2→7F0 in glass and glass ceramics were investi-gated to analyze the local environment around Eu3 . Judd-Ofelt parameters were also calculated from emission spectra, which indicated that the Eu3 ions entered the precipitated CaF2, SrF2, and BaF2 nanocrystallites. Heat treating could not pledge Eu3 ions to coordinate with F- in the precipitated MgF2 nanocrystallites, owing to the smaller radius of Mg2 than that of Eu3 .     

Upconversion Luminescence of Ce^3＋ Doped BK7 Glass by Femtosecond Laser Irradiation

Near-infrared to visible upconversion luminescence was observed in a multicomponent silicate （BK7） glass containing Ce^3 ＋ ions under focused infrared femtosecond laser irradiation. The emission spectra show that the upconversion luminescence comes from the 4f-5d transition of the Ce^3 ＋ ions. The relationship between the intensity of the Ce^3 ＋ emission and the pump power reveals that a three-photon absorption predominates in the conversion process from the near-infrared into the blue luminescence. The analysis of the upconversion mechanism suggests that the upconversion luminescence may come from a three-photon simultaneous absorption that leads to a population of the 5d level in which the characteristic luminescence occurs.     

Effect of alumina content and heat treatment on microstructure and upconversion emission of Er3+ions in oxyfluoride glass-ceramics

The effect of alumina content and heat treatment temperature and time, on microstructure and Er3+ (0.5 mol.%) emission of oxy-fluoride glass-ceramics were investigated in this research. Two values of 1.8 (SA1.8Er0.5) and 2.18 (SA2.18Er0.5) were selected in this re-search for SiO2/Al2O3 ratio. According to DTA results, precursor glasses were heat treated at 630, 660 and 690 °C for 4 h and some glasses were also heat treated at 630 °C for 48 and 72 h. The results indicated that alumina content had significant effect on phase separation and vis-cosity of the glasses. Therefore the size, size distribution, and volume concentration of nano CaF2 crystals which precipitated during the heat treatment depended on alumina content of the glass. Due to the much smaller size of the precipitated CaF2 crystals in the glasses of low alumina content, these samples maintained excellent transparency and had narrower crystal size distribution than the high alumina glasses. The crystal size was increased markedly with the temperature increasing from 630 to 690 °C. On the other hand a slight increase was observed in the crystal size by raising the heat treatment time in both glasses. Results indicated that in low alumina content glass (SA2.18Er0.5) the size of CaF2 nanocrystals was controlled in one order of magnitude. The increase of heat treatment time and temperature led to the incorporation of Er3+ ions into CaF2 crystalline phase, increasing significantly the upconversion intensity. After heat treatment at 690 ℃ for 4 h, atomic force microscope (AFM) re-vealed the development of small crystals with an average size of 80 and 30 nm in SA1.8Er0.5 and SA2.18Er0.5 samples, respectively.     

Thermal and radiative characteristics of oxyfluoride glass singly doped with lanthanide ions

Rare earths-doped oxyfluoride glasses based on germanium oxide and lead fluoride were prepared from commercial raw materials. The glasses with general composition of 50GeO2-(50-x-y)PbO-yPbF2-xLnF3 (Ln=Pr3+-Yb3+), contained different concentrations of optically active dopants (x=0.2 mol.% and 2 mol.%) and PbF2 (y≤15 mol.%). The differential thermal analysis (DTA) was used to determine both thermal characteristic and thermal stability properties of the glasses in the function of the kind of dopant, its concentration, and a glass composition. Characteristic glass temperatures such as glass transition temperature (Tg), glass crystallization temperature (Tc) and temperature corresponding to the maximum of the crystallization rate (Tpc) were evaluated. On the basis of obtained results, the thermal stabilities of glasses under study were evaluated using various thermal stability criteria (Dietzel factor ?T, Saad-Poulain factors H' and S). It was found that the increase in rare earth fluoride contents influenced thermal characteristics when the characteristic temperatures of the individual glass was shifted towards higher values. The effect of the PbF2 content and the kind of rare earth impurity on the glass stability was observed. Absorption spectra of lanthanide-doped glasses were measured at room temperature and used to determine the phenomenological intensity parameters Ωt and next, to estimate radiative properties of lanthanide ions in this matrix. Radiative transition probabilities of luminescent states of Ln3+, branching ratios and radiative lifetimes were determined. The variation of the Ωt along the lanthanide series was presented and discussed.     

Infrared to ultraviolet upconversion luminescence in Nd doped nano-glass-ceramic

Nd^3＋ doped transparent oxyfiuoride glass ceramic containing β-YF3 nanocrystals was prepared and the upconversion luminescence behaviors of Nd^3＋ in the precursor glass and glass ceramic were investigated. Under 796 nm laser excitation, ultraviolet upconversion emissions of Nd^3＋ ions at 354 nm （^4D3/2→^4I11/2） and 382 nm （^4D3/2→^4I11/2） were observed at room temperature. Power dependence analysis demonstrated that three-photon upconversion processes populated the ^4D3/2 excited state. In comparison with those of the precursor glass, the ultraviolet emissions were enhanced by a factor of 500 in the glass ceramic, which was attributed to the change in the ligand field of Nd^3＋ ions and the decrease in phonon energy because of the partition of Nd^3＋ ions into the β-YF3 nanocrystals after crystallization.     

Effect of Crystallization of Li2O-Al2O3-SiO2 Glasses on Luminescence Properties of Nd^3＋ Ions

In the field of solid-state lasers ,it is generallyconsidered that laser action can only be obtained insingle crystals or glasses ,because they ensure lowab-sorption or diffusion of light , which is required toovercome laser threshold . Now, the number of thehost materials has increased withthe addition of a newmaterial group ,glass-ceramics .Transparent glass-ce-ramics may advantageously replace glass lasers in sev-eral applications ranging from microchip lasers andamplifying optical fibers t…     

Local vibration around rare earth ions in alkaline earth fluorosilicate transparent glass and glass ceramics using Eu probe

By heat treating the alkaline earth fluorosilicate glass, transparent glass ceramics containing alkaline earth fluoride nanocrystallites were prepared. The luminescence spectra and phonon sideband associated with the Eu^3＋：^5D2→^7F0 in glass and glass ceramics were investigated to analyze the local environment around Eu^3＋. Judd-Ofelt parameters were also calculated from emission spectra, which indicated that the Eu^3＋ ions entered the precipitated CaF2, SrF2, and BaF2 nanocrystallites. Heat treating could not pledge Eu^3＋ ions to coordinate with F^- in the precipitated MgF2 nanocrystallites, owing to the smaller radius of Mg^2＋ than that of Eu^3＋.     

Temperature sensing behavior of Tm~(3+):~1G_4(a),~1G_4(b) in oxyfluoride glass ceramics containing BaYb_xY_(1-x)F_5 nanocrystals

Tm~(3+)-doped transparent oxyfluoride glass ceramics containing BaYb_xY((1-x))F_5 nanocrystals were prepared via high temperature solid phase melting method,of which up-conversion emission is achieved by the Yb~(3+)-mediated energy transfer process.The required photon number of Tm~(3+)ions emissions in BaYb_xY_((1-x))F_5 nanocrystals was calculated through the luminescence spectra,revealing the strong dependence of energy transfer mechanism on Yb~(3+)ions concentration.Meanwhile,based on the fluore scence intensity ratio technology,the effect of different energy transfer mechanism on the temperature sensitivity was investigated by the temperature-dependent luminescence intensity of thermally coupled energy levels of Tm~(3+):~1G_4(a),~1G_4(b).The obtained sensitivity decreases with the increase of Yb~(3+)ions content,which is mainly attributed to the changes in photon absorption process of Tm~(3+):~1G_4(b).