Up-conversion luminescence of Er~（3＋）-doped and Yb~（3＋）/Er~（3＋） co-doped 12CaO·7Al_2O_3 poly-crystals

The optical properties of Er3+-doped and Yb3+/Er3+ co-doped 12CaO·7Al2O3 (C12A7) poly-crystals, synthesized by high temperature solid state method, were investigated in detail. For Er3+-doped and Yb3+/Er3+ co-doped C12A7 poly-crystals, two main emission bands centered around 530/550 nm (green) and 660 nm (red) were observed under 980 nm diode laser excitation via an up-conversion process. The intensity of green up-conversion emission had a strong increase in Er3+ (1.0 mol.%, 1.5 mol.%, 3.0 mol.%), and the intensity ratio of red to green up-conversion emission had an increase in Yb3+ (1.0 mol.%, 2.0 mol.%, 10. 0 mol.%)/Er3+ (fixed at 1.0 mol.%). This detailed study of the up-conversion processes allowed us to identify the dominant up-conversion mechanisms in Er3+-doped and Yb3+/Er3+ co-doped C12A7 poly-crystals.     

Up-conversion luminescence of Er~(3+)-doped and Yb~(3+)/Er~(3+) co-doped 12CaO·7Al_2O_3 poly-crystals

The optical properties of Er3+-doped and Yb3+/Er3+ co-doped 12CaO·7Al2O3 (C12A7) poly-crystals, synthesized by high temperature solid state method, were investigated in detail. For Er3+-doped and Yb3+/Er3+ co-doped C12A7 poly-crystals, two main emission bands centered around 530/550 nm (green) and 660 nm (red) were observed under 980 nm diode laser excitation via an up-conversion process. The intensity of green up-conversion emission had a strong increase in Er3+ (1.0 mol.%, 1.5 mol.%, 3.0 mol.%), and the i...     

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.     

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） GdFy0.1NdF3.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 diameter 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 Tm^3＋ up-conversion luminescence after laser irradiation 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.     

Up-conversion luminescence properties of Yb^3＋ and Ho^3＋ co-doped Bi3.84W0.16O6.24 powder synthesized by hydrothermal method

Using polyethylene glycol (PEG) as the surfactant, Bi3.84W0.16O6.24 up-conversion luminescence nano-crystal co-doped with Yb3+ and Ho3+ ions was synthesized by the hydrothermal method. The structure and properties of luminescence powder were studied by X-ray diffraction (XRD) and scanning electron microscope (SEM). It was of cubic system when the sample was synthesized at a low temperature and the particle size was about 30 nm. The results showed that adding surfactants was useful to improve the powder agglomeration and the grain crystal was spherical. The green emission peak at 546 nm and red emission peak at 655 nm, corresponding to the ( 5F4, 5S2)→ 5 I 8 and the 5 F 5 → 5 I 8 transitions of Ho 3+ , respectively, were simultaneously observed at room temperature under excitation of 980 nm semiconductor laser. The up-conversion luminescence intensity was the strongest when the concentration ratio of Yb3+ /Ho3+ was 6:1 and the concentration of Ho 3+ ion was 1.5 mol.%. The up-conversion mechanism was also studied. The green and red emission peaks were the two-photon absorption according to the relationship between the pump power and the luminescence intensity.     

50GeSe_2-25In_2Se_3-25CsI glass doped with Tm~(3+),Tm~(3+)/Ho~(3+) and Tm~(3+)/Er~(3+) foramplifiers working at 1.22 μm

Se-based chalcohalide glass of 50GeSe2-25In2Se3-25CsI was prepared.The thermal and optical characterizations revealed that thishost was thermally and optically superior for practical applications.Strong emission centered at 1.22 μm was observed in all Tm3+ single-doped,Tm3+/Ho3+ and Tm3+/Er3+ co-doped samples with an excitation of 808 nm wavelength.The emission was attributed to the Tm3+:3H5→3H6 transition.The co-doping of Ho3+ or Er3+ largely broadened the width and slightly strengthened the intensity of t...     

Preparation and characterization of Er3＋-Yb3＋-Ce3＋ co-doped transparent glass ceramic containing nano Cas（PO4）3F crystals

A transparent glass ceramic tri-doped with Ce3+/Er3+/Yb3+ was fabricated by the high-temperature melting technique and following heat-treatment.X-ray diffraction and transmission electron microscope results demonstrated that Ca5(PO4)3F(FAP) nanocrystals,possessed with preferable emission performances for the 1.54 m transition for doping Er3+,were homogeneously precipitated among the glass matrix with a mean size of 30 nm.Addition of Ce3+ greatly enhanced 1.54 m fluorescence of Er3+ by the cross relaxation energy transfer between Er3+ and Ce3+.Meanwhile,incorporation of Ce3+ dramatically decreased the visible upconversion emission intensity of glass ceramic than that of glass,suggesting that Ce3+ might incorporate into the FAP nanocrystals.The properties of this transparent glass ceramic showed the potential application as an efficient 980 nm pumped infrared laser medium.     

Effect of glass network modifier R2O (R=Li,Na and K) on upconversion luminescence in Er3+/Yb3+ co-doped NaYF4 oxyfluoride glass-ceramics

The effect of glass network modifier R2O (R=Li, Na, K) on upconversion luminescence in Er3+/Yb3+ co-doped NaYF4 oxyfluoride glass-ceramics was investigated. NaYF4 nanocrystals with different sizes were...     

Preparation and luminescence properties of Eu3+ doped oxyfluoride borosilicate glass ceramics

Oxyfluoride borosilicate glass with the molar composition of 60SiO2-15B2O3-15Na2O-8CaF2-2NaF-0.25Eu2O3 was synthesized by a traditional glass melting method. Glass ceramics containing CaF2 nanocrystals were prepared by heat treating the glass samples at a tem-perature in the range of 620-680 °C. The results of X-ray diffraction (XRD) indicated that the average crystallite size and the lattice constant of CaF2 nanocrystals increased with the heat treatment temperature increasing. The luminescence spectra showed that the emission intensity of Eu3+ doped glass ceramics was stronger than that of the glass matrix, and increased with the heat treatment temperature increasing. The left edge of excitation band shifted to shorter wavelength in the glass ceramics. The local environments of Eu3+ ions in the glass and glass ceram-ics were different.     

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.     

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.     

Quenching mechanism of Er^3＋ emissions in Er^3＋-and Er^3＋/Yb^3＋-doped SrAl12O19 nanophosphors

Nanoscaled SrAl12O19:Er3+ and SrAl12O19:Yb3+,Er3+ phosphors were synthesized by a combustion method.The emission intensities of every sample were compared by a new method with the emission of codoped Gd3+ ions as a reference.Compared with their bulk material prepared by the solid-state reaction method,a higher Er3+ quenching concentration,as high as 20%,was observed in the nanoscaled phosphors for both visible(VIS) and near infrared(NIR) emissions.The higher quenching concentration in both VIS and NIR regions for nanoscaled samples are related to the structure characteristics of the nano particles.The influence of the introduction of Yb3+ ions on the emission spectra intensity was also investigated and discussed.     

Luminescence properties of Tm^3＋/Yb^3＋, Er^3＋/Yb^3＋ and Ho^3＋/Yb^3＋ activated calcium tungstate

CaWO4 phosphor activated by the Tm3+/Yb3+,Er3+/Yb3+ and Ho3+/Yb3+ ions were synthesized by a traditional high-temperature solid-state method.The crystal structures and morphologies of the products were characterized by X-ray powders diffraction method(XRD) ,infrared spectra(FT-IR) and scanning electron microscopy(SEM) .The samples were found to show up-conversion luminescence properties.CaWO4 doped with Tm3+/Yb3+ showed blue luminescence characteristic of Tm(III) ion in the range of 460-485 nm,corresponding to the 1G4→3H6 electronic transition.CaWO4 doped with Er3+/Yb3+ showed strong green luminescence at 510-565 nm(2H11/2,4S3/2→4I15/2) and weak red luminescence at 640-685 nm(4F9/2→4I15/2) of Er(III) ion.CaWO4 doped with Ho3+/Yb3+ phosphor emitted green luminescence at 525-560 nm(5S2,5F4→5I8) and red luminescence at 630-670 nm(5F5→5I8) and at 730-770 nm(5S2,5F4→5I7) ,which is the characteristic of Ho(III) ion.     

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.     

Green up-conversion luminescence in Yb^3＋-Pr^3＋ co-doped BaRE2ZnO5（RE=Y,Gd）

Yb3＋and Pr3＋co-doped BaRE2 ZnO5（RE=Y,Gd） up-conversion（UC） phosphors were successfully synthesized by a modified sol-gel method.The processing parameters and optimal concentration of Pr3＋and Yb3＋were determined.The structures and luminescent properties of samples were characterized by X-ray diffraction（XRD） and photoluminescence spectra（PL）.With the excitation of 980 nm laser diode,UC spectra showed five prominent emission bands centered at 484,514,546,656 and 670 nm,which were attributed to the1I6 →3H4,3P1 →3H4,3P0 →3H5,3P0 →3F2 and3P0 →3F3 transitions of Pr3＋,respectively.In the light of the pump power dependence,the possible UC mechanism in Yb3＋and Pr3＋co-doped BaRE2 ZnO5（RE=Y,Gd） was proposed and discussed.     

Upconversion luminescence ofNaYF4：Yb,Er nanocrystals with high uniformity

The NaYF4：Yb,Er nanocrystals were synthesized via the thermal decomposition ot metal oleate precursors, lhe nanocrys- tals in hexagonal structure were highly uniform and in size of 25 nm. The bright upconversion luminescence was observed under the excitation of 980 nm laser and the upeonversion emission spectra were investigated at different pump powers. The emission intensity ratio of red light to green light linearly increased with pump power increasing. This result indicated that there existed a large threshold power of saturation pump for the first excitation state in NaYFa：Yb,Er nanocrystals comparing to that in bulk material.     

Preparation and photoluminescence of Eu-doped oxyfluoride borosilicate glass ceramics

Eu-doped transparent oxyfluoride borosilicate glass ceramics containing Ba2GdF7 nanocrystals were prepared by controlling crys-tallization of melt-quenched glass fabricated under a reductive atmosphere.In the oxyfluoride borosilicate glass ceramics,the mean crystal size of Ba2GdF7 nanocrystals was about 30 nm,which could be observed by X-ray diffraction(XRD) and transmission electron microscopy analysis.The photoluminescence spectra of the samples excited at 392 nm showed that,besides the characteristic sharp emissions of Eu3+ ions,a very intense broadband emission of Eu2+ ions centered at 450 nm appeared.The photoluminescence intensity of Eu3+ and Eu2+ ions in the glass ceramics was much stronger than that in the as-made precursor.The long decay lifetimes of Eu3+ and Eu2+ ions evidenced the partitions of Eu3+ and Eu2+ ions into the Ba2GdF7 nanocrystals.The energy transfer from Gd3+ ions to Eu3+ and Eu2+ ions was confirmed by the excita-tion and emission spectra.     

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.     

Spectral variations of Ca3Sc2Si3O12:Ce phosphors via substitution and energy transfer

The luminescence intensity of emission peak at around 525 nm decreased in the Ce3+ and Er3+ co-doped Ca3Sc2Si3O12 phosphors. Mg2+ ion, which was likely incorporated into the Sc3+ position of the host crystal, was co-doped to adjust the crystal field and compensate for the excess positive charge due to the doping of Ce3+. The green emission belonged to the 5d→4f transition of Ce3+ moved toward longer wavelength by addition of Mg2+ in Ce3+ and Er3+ co-doped Ca3Sc2Si3O12 phosphor, which could increase the brightness of the phosphor. However, the position of weakening of luminescence intensity at around 525 nm remained basically unchanged by increasing the amount of Mg2+. The results showed that the weakening of luminescence intensity at around 525 nm caused by the absorption of Er3+, which had little influence on the environment of the crystal field.