Abnormal Visible Luminescence Mechanism of Tb^3＋-Yb^3＋ Codoped SiOu-Al2O3-CaF2 Glass Studied by Time-Resolved Spectra

The upconversion energy transfer mechanism in Tb^3＋-Yb^3＋ co-doped SiO2-Al2O3-CaF2 glass is investigated by time-resolved spectra. The effect of donor ion Yb^3＋ is involved in the dynamic decay behavior of acceptor ion Tb^3＋, which provides direct proof for the energy transfer from Yb^3＋ to Tb^3＋. The pump power dependence curves show that the upconversion luminescence is a two-photon process. The measured decay curves of the 5D4 state （Tb^3＋） contain two parts： a slow decay process corresponding to its radiation, and a fast one with a decay parameter approximately twice the lifetime of the ^2F5/2 state （Yb^3＋ ）. The fast decay process is contradictory to the generally accepted cooperative sensitization upconversion rate equation model. Since the effect of the host environmental is excluded by comparative experiments, we believe that there should be another energy transfer mechanism in Tb^3＋-Yb^3＋ co-doped SiO2-Al2O3-CaF2 glass in addition to the cooperative sensitization process.     

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.     

Broadband and High Efficient 1530 nm Emission from Oxyfluoride Glass Ceramics Codoped with Er3＋ and Yb3＋ Ions

The emission at 1530nm and its applications in optical communications are discussed. The efficient width of the emission band △eff, which is up to 91 nm, is larger as compared with silica-based glass, bismuth glass and ZrF4-BaF2-LaFa-AIF3-NaF （ZBLAN） glass doped by Er^3＋ ions. Under the excitation of 785 nm laser, the emission integral intensity of 153Onto increases about five times in the glass ceramics higher than that in the glass. This is explained by the quantum cutting process by two-photon emission with phonon assistance. The results indicate that the glass ceramics are a promising candidate for developing broadband optical amplifiers in wavelength-division multiplexed systems.     

White light generation of glass ceramics containing Ba_2LaF_7：Eu~（2＋）,Tb~（3＋） and Sm~（3＋） nanocrystals

The Eu 2＋ /Tb 3＋ /Sm 3＋ co-doped oxyfluoride glass ceramics containing Ba2LaF7 nanocrystals are prepared in the reducing atmosphere.The X-ray difiraction results show that Eu 2＋ ,Tb 3＋ and Sm 3＋ ions are enriched into the precipitated Ba2LaF7 nanophase after the annealing process.It deduces efficient energy transfers from Eu 2＋ to Tb 3＋ and Sm 3＋ and intenses warm white luminescence of the glass ceramics. Comparing with the glass,the luminescence quantum yield of the glass ceramics is also enlarged by about 3 times.This demonstrates the potential white light-emitting diode application of the glass ceramics produced in this letter.     

Er^3＋/Tm^3＋/Yb^3＋ tridoped oxyfluoride glass ceramics with efficient upconversion white-light emission

A novel Tm^3＋/Yb^3＋ triply-doped glass ceramics containing BaF2 nano-crystals are successfully prepared. Fluoride nanocrystals BaF2 are successfully precipitated in glass matrix, which is affirmed by the X-ray diffraction results. The intense blue （476 nm）, green （543 nm）, and red （656 nm） emissions of the glass ceramics are simultaneously observed at room temperature under 980-am excitation, and the emission luminescence intensity increases significantly compared with the precursor glass, which is attributed to the low phonon energy of fluoride nanocrystals when rare-earth ions are incorporated into the precipitated BaF2 nanocrystals. Under 980-nm excitation at 400 mW, the international commission on illumination （CIE） chromaticity coordinate （X = 0.278, Y = 0.358） of the tridoped oxyfluoride glass ceramics＇ upconversion emissions is close to the standard white-light illumination （X = 0.333, Y= 0.333）. The results indicate that Tm^3＋/Yb^3＋ triply doped glass ceramics can act as suitable materials for potential three-dimensional displays applications.     

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.     

Spectroscopic properties and mechanism of Tm^3＋/Er^3＋/Yb^3＋ co-doped oxyfluorogermanate glass ceramics containing BaF2 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.     

Red Up-Conversion Luminescence Process in Oxyfluoride Glass Ceramics Doped with Er^3＋／Yb^3＋

The phonon-assisted quantum cutting (PQC) model is presumed to clarify the red up-conversion luminescence process in Er^3 /yb^3 co-doped glass ceramics by the excitation and emission spectra. The red up-conversion luminescence of Er^3 ions mainly comes from three-photon absorption by the PQC process when the rare earth ions are doped in the g/ass ceramics and excited by 98Ohm pumped-laser. Er^3 ions absorb three-photons and relax to the ^4G11/2 state and then emit red up-conversion luminescence by the PQC process. The factor coefficient for the relation of pump-laser power and up-conversion intensity (P-I) is found by the analysis of excitation spectra of the red luminescence, which plays a major role to understand the true red up-conversion luminescence process. The new P-I relation is explained by the model of PQC.     

Nd^3＋, Yb^3＋ and Ho^3＋ Codoped Oxyfluoride Glass Ceramics with High Efficient Green Upconversion Luminescence

New oxyfluoride g/asses and glass ceramic codoped with Nd3 , Yb3 and Ho3 were prepared. The x-raydiffraction analysis revealed that the heat treatments of the oxyfluoride g/asses could cause the precipitationof (Nd^3 , Yb^3 , Ho^3 )-doped fluorite-type crystals. Very strong green up-conversion luminescence due to theHo3 : (^5F4, ^5S2)→ ^5I8 transition under 800-nm excitation was observed in these transparent glass ceramics.The intensity of the green up-conversion luminescence in a 1-mo1% YbF3-containing glass ceramic was found tobe about 120 times stronger than that in the precursor oxyfluoride glass. The reason for the highly efficient Ho^3 up-conversion luminescence in the oxyfluoride g/ass ceramics is discussed.     

Infrared-to-green upconversion luminescence and mechanism of Ho3+, Nd3+ and Yb3+ ions in oxyfluoride glass ceramics

New oxyfluoride glasses and glass ceramics co-doped with Nd^{3+}, Yb^{3+} and Ho^{3+} were prepared. The upconversion of infrared radiation into green fluorescence has been studied for Nd^{3+}, Yb^{3+} and Ho^{3+} in the transparent oxyfluoride glass ceramics. At room temperature very strong green upconversion luminescence due to the Ho^{3+}: ({}^5F_4, {}^5S_2)→{}^5I_8 transition under 800 nm excitation was observed in the glass ceramics. The intensity of the green upconversion luminescence in a 1mol% YbF_3-containing glass ceramic was found to be about 120 times stronger than that in the precursor oxyfluoride glass. The reason for the highly efficient Ho^{3+} upconversion luminescence in the oxyfluoride glass ceramics is discussed. The upconversion mechanism is also investigated.     

Luminescence Spectra of YGG：RE^3＋, Bi^3＋ （RE = Eu and Tb） and Energy Transfer from Bi^3＋ to RE^3＋

We investigate the luminescence properties of Bi^3＋ and RE^3＋ （RE = Tb or Eu） in a Y3Ga5O12 （YGG） host system. The additional doping of Bi^3＋ can enhance the luminescence of Th^3＋ or Eu^3＋ in this host. Energy transfer from Bi^3＋ to Tb^3＋ and Eu^3＋ is observed and the mechanism of energy transfer is investigated. Mechanism of energy transfer can be explained as electric multipole interaction since the Bi^3＋ emission band and Tb^3＋ or Eu^3＋ excitation band overlaps and the Bi^3＋ emission intensity decreases while the intensity of Tb^3＋ or Eu^3＋ increases with the increase of Tb^3＋ or Eu^3＋ concentration. Therefore, Bi^3＋ ion is a kind of efficient sensitizer to the Tb^3＋ and Eu^3＋ activators in the Y3Ga5O12 host.     

Intense Green Upconversion Luminescence in Er^3＋：Yb^3＋ Codoped Fluorophosphate Glass Ceramic Containing SrTe5O11 Nanocrystals

Er^3＋ ：Yb^3＋ codoped tellurite-fluorophosphate （TFP） glass ceramic exhibits much stronger upconversion luminescence. The intensity of the 540nm green light and 651 nm red light of the TFP glass ceramic is 120 times and 44 times stronger than that of the fluorophospahte （FP） glass, respectively. XRD analysis shows that the nanocrystal in TFP glass ceramic is SrTe5O11. TFP glass ceramic also displays much higher upconversion fluorescence lifetime and crystallization stability. The narrow and strong peak at 540nm is very ideal for practical upconversion luminescence realization. This work is a new trial for exploring non-PbF2 involved nanocrystal upconversion glass ceramics.     

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%.     

Vacuum Ultraviolet Excited Photoluminescence Properties of Novel Na3Y9O3（BO3）8：Tb^3＋ Phosphor

The novel vacuum ultraviolet （VUV） excited Na3 Y9O3 （BO3）8：Tb^3＋ （NYOB：Tb^3＋） green phosphor is prepared. Strong VUV photoluminescence and high quenching concentration of Tb^3＋ （20 wt%） are observed in NYOB： Tb^3＋ and the strong emission are correlated with the unique layer-type structure of NYOB. All the characteristic 4 f - 5d transitions of Tb^3＋ and the host absorption band in VUV region are identified in the excitation spectrum. Based on the results, the energy levels scheme of Tb^3＋ in NYOB：Tb^3＋ is first established. This newly developed NYOB：Tb^3＋ phosphor shows excellent optical properties when compared with the commercial Zn2SiO4：Mn^2＋ and would be a potential VUV-excited green phosphor.     

Efficient Fibre Amplifiers Based on a Highly Er3＋/Yb3＋ Codoped Phosphate Glass-Fibre

Highly Er3＋ /yb3＋-codoped single-mode phosphate glass fibre is fabricated by the rod-in-tube technique. The performances of high-concentration Er3＋ /yb3＋-codoped phosphate glass fibre amplifiers are investigated and discussed. An efficient optical fibre amplifier with a gain of 12.6 dB based on a 3.0 cm long Era＋ /ybe＋-codoped phosphate glass fibre is demonstrated under a dual-pump configuration with two 976 nm fibre-pigtail laser diodes, which make it attractive for compact Er3＋-doped fibre amplifiers. The obtedned noise figures of signal wavelength from 1525 to 1565nm are less than 6.0dB. Gain saturation behaviour at 1535nm is also investigated, and the obtained saturation output power is larger than 10 dBm.     

Sol-gel法制备Er3+-Yb3+共掺杂Al2O3粉末光致发光特性

采用异丙醇铝[Al(OC₃H₇)₃]为前驱体,溶胶-凝胶(Sol-gel)法制备Er³⁺-Yb³⁺共掺杂Al₂O₃粉末.实验结果表明:900 ℃烧结的粉末为固溶Er³⁺、Yb³⁺的γ-(Al,Er,Yb)₂O₃相和少量θ-(Al,Er,Yb)₂O₃相的混合物.Er³⁺-Yb³⁺共掺杂Al₂O₃粉末具有中心波长为1.533 μm的光致发光(PL)特性.1 mol % Er³⁺和1 mol% Yb³⁺共掺杂的Al₂O₃粉末的PL强度较1 mol % Er³⁺掺杂提高2倍,半峰宽从53 nm增加到63 nm.随泵浦功率的提高,PL强度呈线性增加后渐呈饱和趋势.     

Self-Starting Passively Mode-Locked Er^3＋/Yb^3＋ Codoped Phosphate Glass All-Fibre Ring Laser

A self-starting, passively mode-locked all-fibre ring laser based on the homemade Er^3＋/Yb^3＋ codoped phosphate glass fibre is reported. Dual-pump sources were used to achieve the mode-locked operation in the experiment. The fundamental mode-locked pulse repetition rate is 10.67MHz. The pulse duration, assumed as the fit of hyperbolic secant pulse shape, is 5.82ps. We also observe the multi-pulse output of the fibre laser.     

Quantum cutting downconversion by cooperative energy transfer from Bi3+ to Yb3+ in Y2O3 phosphor

Bi~(3+) and Yb~(3+) codoped cubic Y2O3 phosphors are prepared by pechini sol-gel method.Strong near-infrared (NIR) emission around 980 nm from Yb~(3+)(2F5/2 → 2F7/2) is observed under ultraviolet light excitation.A broad excitation band ranging from 320 to 360 nm,owing to the 6s 2 →6s6p transition of Bi~(3+) ions,is recorded when the Yb~(3+) emission is monitored,which suggests a very efficient energy transfer from Bi~(3+) ions to Yb~(3+) ions.The Yb~(3+) concentration dependences of both the Bi~(3+) and the Yb~(3+) emissions are investigated.The decay curve of Bi ~(3+) emission under the excitation of 355 nm pulse laser is used to explore the Bi~(3+) →Yb~(3+) energy transfer process.Cooperative energy transfer (CET) is discussed as a possible mechanism for the near-infrared emission.     

Intrinsic Bistability and Critical Slowing in Tm^3＋/Yb^3＋ Codoped Laser Crystal with the Photon Avalanche Mechanism

We present theoretically a novel intrinsic optical bistability （IOB） in the Tm^3＋ /Yb^3＋ codoped system with a photon avalanche mechanism. Numerical simulations based on the rate equation model demonstrate distinct 10B hysteresis and critical slowing dynamics around the avalanche thresholds. Such an 10B characteristic in Tm^3＋ /Yb^3＋ eodoped crystal has potential applications in solid-state bistable optical displays and luminescence switchers in visible-infrared spectra.     

Characteristics of Cladding-Pumped Short Er3+/Yb3+ Codoped Single Mode Phosphate Glass Fibre

We experimentally investigate the laser characteristics of a series of short pieces of newly-developed Er³⁺/Yb³⁺ codoped single mode phosphate glass fibres via the cladding pump of a 976nm multimode laser diode. A stablecontinuous-wave single transverse mode laser with over 85mW at 1553nm is generated from a 5.5-cm-long active fibre. Single mode laser output power per unit length is up to 15mW/cm. Moreover, the slope efficiency is 11.8% when the pump power is below 940mW and the 3dB linewidth is 0.06nm at the maximum pump power. The numerical simulation results show that the laser emission slope efficiency can exceed 20% by means of increasing the coupling efficiency of the pump to the fibre core further.