Investigation of spectroscopic properties and thermal stability of Er/Yb-co-doped Bi2O3-B2O3-Ga2O3 glasses

A series of Er³⁺/Yb³⁺-co-doped 60Bi₂O₃-(40−x) B₂O₃ -xGa₂O₃ (BBGA x=0, 4, 8, 12, 16 mol%) glasses have been prepared. The absorption spectra, emission spectra, fluorescence lifetime of Er³⁺:⁴I_13/2 level and thermal stability were measured and investigated. Three Judd-Ofelt intensity parameters Ω_t (t=2,4,6) (Ω₂=(4.67-5.93)×10⁻²⁰ cm², Ω₄=(1.50-1.81)×10⁻²⁰ cm², Ω₆=(0.92-1.17)×10⁻²⁰ cm²) of Er³⁺ ions were calculated by Judd-Ofelt theory. It is found that the Ω₆ first increases with the increase of Ga₂O₃ content from 0 to 8 mol% and then decreases, which is mainly affected by the number of non-bridging oxygen ions of the glass network. The high peak of stimulated emission cross-section () of Er³⁺: ⁴I_13/2→⁴I_15/2 transition were obtained according to McCumber theory and broad full width at half maximum (FWHM=69-76 nm) of the ⁴I_13/2→⁴I_15/2 transition of Er³⁺ ions were measured. The results indicate that these new BBGA glasses can be used as a candidate host material for potential broadband optical amplifiers.     

Spectroscopic investigations of Nd-, Er-, Er/Yb-, and Tm-ions doped SiO2-Al2O3-CaF2-GdF3 glasses

This paper reports on the absorption, visible and near-infrared luminescence properties of Nd³⁺, Er³⁺, Er³⁺/2Yb³⁺, and Tm³⁺ doped oxyfluoride aluminosilicate glasses. From the measured absorption spectra, Judd-Ofelt (J-O) intensity parameters (Ω₂, Ω₄ and Ω₆) have been calculated for all the studied ions. Decay lifetime curves were measured for the visible emissions of Er³⁺ (558 nm, green), and Tm³⁺ (650 and 795 nm), respectively. The near infrared emission spectrum of Nd³⁺ doped glass has shown full width at half maximum (FWHM) around 45 nm (for the ⁴F_3/2→⁴I_9/2 transition), 45 nm (for the ⁴F_3/2→⁴I_11/2 transition), and 60 nm (for the ⁴F_3/2→⁴I_13/2 transition), respectively, with 800 nm laser diode (LD) excitation. For Er³⁺, and Er³⁺/2Yb³⁺ co-doped glasses, the characteristic near infrared emission bands were spectrally centered at 1532 and 1544 nm, respectively, with 980 nm laser diode excitation, exhibiting full width at half maximum around 50 and 90 nm for the erbium ⁴I_13/2→⁴I_15/2 transition. The measured maximum decay times of ⁴I_13/2→⁴I_15/2 transition (at wavelength 1532 and 1544 nm) are about 5.280 and 5.719 ms for 1Er³⁺ and 1Er³⁺/2Yb³⁺ (mol%) co-doped glasses, respectively. The maximum stimulated emission cross sections for ⁴I_13/2→⁴I_15/2 transition of Er³⁺ and Er³⁺/Yb³⁺ are 10.81×10⁻²¹ and 5.723×10^-21 cm². These glasses with better thermal stability, bright visible emissions and broad near-infrared emissions should have potential applications in broadly tunable laser sources, interesting optical luminescent materials and broadband optical amplification at low-loss telecommunication windows.     

Waveguiding and photoluminescence in Er-doped Ta2O5 planar waveguides

The optimization of erbium-doped Ta₂O₅ thin film waveguides deposited by magnetron sputtering onto thermally oxidized silicon wafer is described. Optical constants of the film were determined by ellipsometry. For the slab waveguides, background losses below 0.4 dB/cm at 633 nm have been obtained before post-annealing. The samples, when pumped at 980 nm yielded a broad photoluminescence spectrum (FWHM∼50 nm) centred at 1534 nm, corresponding to ⁴I_13/2-⁴I_15/2 transition of Er³⁺ ion. The samples were annealed up to 600 °C and both photoluminescence power and fluorescence lifetime increase with post-annealing temperature and a fluorescence lifetime of 2.4 ms was achieved, yielding promising results for compact waveguide amplifiers.     

Spectral performance and intensive green upconversion luminescence in Er/Yb-codoped NaY(WO4)2 crystal

Using Czochralski (CZ) pulling method, an Er³⁺/Yb³⁺-codoped NaY(WO₄)₂ crystal was prepared. Absorption spectra, emission spectra and excitation spectra of this crystal were measured at room temperature. Some optical parameters, such as intensity parameters, spontaneous emission probabilities and lifetimes, were calculated from absorption spectra with Judd-Ofelt (J-O) theory. Upconversion luminescence excited by a 970 nm diode laser was studied. In this crystal, green upconversion luminescence is particularly intensive. Energy transfer mechanisms that play an important role in upconversion processes were analyzed. Two cross-relaxation processes: ⁴G_11/2 + ⁴I_9/2 → ²H_11/2 (or ⁴S_3/2) + ²H_11/2 (or ⁴S_3/2), and ⁴G_11/2 + ⁴I_15/2 → ²H_11/2 (or ⁴S_3/2) + ²I_13/2, which contribute to the intensive green luminescence under 378 nm excitation, were put forward. Background energy transfer ⁴G_11/2(Er³⁺) + ²F_7/2(Yb³⁺) → ⁴F_9/2(Er³⁺) + ²F_5/2(Yb³⁺) was also demonstrated.     

Optical properties of Er in MoO3-Bi2O3-TeO2 glasses

Erbium-doped MoO₃−Bi₂O₃−TeO₂ (MBT) glasses suitable for broadband optical amplifier applications have been fabricated and characterized optically. The maximum phonon band of undoped glasses is at 915 cm⁻¹, and the emission from the Er³⁺: ⁴I_13/2 → ⁴I_15/2 transition locates around 1.53 μm with a full width at half maximum (FWHM) of ∼80 nm. The lifetime and quantum efficiency of the ⁴I_13/2 level are 2.13 ms and ∼90%, respectively. Under the same measurement condition, the upconversion emission intensities at 550 nm in Er³⁺-doped MBT glasses is about 30 times weaker than that in Er³⁺-doped Na₂O−ZnO−TeO₂ (NZT) glasses.     

Optical detection of near infrared femtosecond laser-heating of Er-doped ZnO-Nb2O5-TeO2 glass by green up-conversion fluorescence of Er ions

The green up-conversion fluorescence of Er³⁺ ions doped in an nonlinear optical ZnO-Nb₂O₅-TeO₂ glass was observed by using 800 nm excitation from a regenerative femtosecond (fs) Ti:Sapphire laser. The detailed analysis on two fluorescence lines at 526 nm (²H_11/2-⁴I_15/2) and 548 nm (⁴S_3/2-⁴I_15/2) revealed the fs laser heating of the multi-component TeO₂-based glass, which was possibly due to its nonlinear absorption of the host glass via the imaginary part of the third-order optical susceptibility (χ⁽³⁾). The result was compared with that of a Er³⁺-doped aluminosilicate glass under the same irradiation condition. When the fs laser was irradiated to the multicomponent TeO₂-based glass in the power density of 150 TW/cm², the laser spot was heated up to ∼520 K, which however was still less than the glass transition temperature (T_g=688 K). This technique provides a useful sensing method of laser spot temperature even inside transparent materials.     

Effect of Ce on the spectroscopic properties in Er doped TeO2-GeO2-Nb2O5-Li2O glasses

The Ce³⁺ ion was introduced into Er³⁺ doped TeO₂-GeO₂-Nb₂O₅-Li₂O (TGNL) glass to improve the 1.5 μm fluorescence characteristics. As increasing of Ce³⁺ concentration, the lifetime of Er³⁺:⁴I_11/2 level is shortened form 360 to 225 μs, while the Er³⁺:⁴I_13/2 level remains unchanged. Accordingly, the upconversion fluorescence (blue, green and red) was quenched. Improved 1.5 μm emission is obtained and the reason is ascribed to the increase of nonradiative rate between the ⁴I_11/2 and ⁴I_13/2 level of the Er³⁺ ions.     

Comparative investigation on spectroscopic properties of Er between Ce-doped and B2O3-added bismuth glasses

The comparative investigation on the spectroscopic properties of Er³⁺ in low phonon energy Bi₂O₃-GeO₂-Ga₂O₃-Na₂O glasses codoped with Ce³⁺ ion and added with B₂O₃ component, respectively, is presented. With increasing Ce₂O₃ content from 0 to 0.8 mol% or B₂O₃ content from 0 to 15 mol%, the lifetime of Er³⁺:⁴I_11/2 level decreases dramatically from 607 to 283 μs or to 197 μs, and the upconversion fluorescence is quenched in both glass samples. The nonradiative energy transfer from Er³⁺:⁴I_11/2→Ce³⁺:²F_5/2 or the enhanced multiphonon relaxation process together with the energy transfer between Er³⁺ and OH⁻ groups are, respectively, responsible for the results. Meanwhile, the lifetime of ⁴I_13/2 level remains almost unchanged in Er³⁺/Ce³⁺-codoped glasses whereas it decreases rapidly in B₂O₃-added cases. As a result, Er³⁺/Ce³⁺ codoping improves the 1.5 μm fluorescence emission intensity, however, B₂O₃ addition has a negative effect on it. The research results indicate that the Er³⁺/Ce³⁺-codoped bismuth glasses will be preferable for obtaining efficient 980 nm pumped EDFA.     

Green and red up-conversion emissions of Er-Yb-codoped Al2O3 powders prepared by the nonaqueous sol-gel method

The 1 mol% Er³⁺- and 0-20 mol% Yb³⁺-codoped Al₂O₃ powders have been prepared by the nonaqueous sol-gel process using aluminum isopropoxide as precursor, acetylacetone as chelating agent, nitric acid as catalyzer, and hydrated erbium and ytterbium nitrate as dopant under isopropanol environment. The two crystalline types of doped Al₂O₃, γ and θ, and a stoichiometric compound, (Yb,Er)₃Al₅O₁₂, were obtained for all the Er³⁺-Yb³⁺-codoped Al₂O₃ powders at the sintering temperature of 1000 °C. The maximal intensity of both the green and red up-conversion emissions centered at about 523, 545, and 660 nm was observed for the 1 mol% Er³⁺- and 10 mol% Yb³⁺-codoped Al₂O₃ powders. The intensity ratio of the red to green up-conversion emission (I_red/I_green) increased with increasing the Yb³⁺ doping concentration for the Er³⁺-Yb³⁺-codoped Al₂O₃ powders. Furthermore, the intensity ratio of the green up-conversion emission at about 523 to 545 nm (I₅₂₃/I₅₄₅) was proportional to the Yb³⁺ doping concentration and pump electric current, which was associated with the elevated temperature of powders.     

Effect of hydroxyl groups on Er doped Bi2O3-B2O3-SiO2 glasses

A series of Er³⁺-doped Bi₂O₃-B₂O₃-SiO₂-Na₂O glasses with different hydroxyl groups were prepared and the interaction between the Er³⁺ ions and OH groups was investigated. Infrared spectra were measured in order to calculate the exact content of OH groups in samples. The observed increase of the fluorescence lifetime with the oxygen bubbling time has been related to the reduction in the OH content concentration evidenced by infrared (IR) absorption spectra, which confirmed that the OH groups were dominant quenching centers of excited Er³⁺ and a cause of concentration quenching of 1.5 μm band emission. Various nonradiative decay rates from ⁴I_13/2 of Er³⁺ with the change of OH content were determined from the fluorescence lifetimes and radiative decay rates, which were calculated on the basis of Judd-Ofelt theory.     

Inhomogeneous broadening of the dynamically split Kramers spectral line and up-conversion in the pair and quartet centers in CaF2:Nd

The site-selective and time-resolved fluorescence laser spectroscopy and kinetic measurements with high spectral and nanosecond temporal resolution was applied to analyze the high-energy wing of the M and N absorption bands of the ⁴I_9/2(1)→⁴G_5/2(1) crystal-field (CF) transition in a CaF₂:Nd³⁺ (0.6 wt%) crystal at 4.2 K. It was found that at helium temperatures the dynamically split spectral line assigned as the ⁴I_9/2(1)→⁴G_5/2(1) (CF) transition of coherently coupled Nd³⁺ ions in the pair M- and quartet N-centers of CaF₂:Nd³⁺ (0.6 wt%) is inhomogeneously broadened. It consists of the pair M- and quartet N-centers with at least 0.1 A variation of the positions of the fluorescence-excitation spectral lines registered at the ⁴F_3/2(1)→⁴I_9/2(1) CF transition. Small fluorescence-lifetimes variation of the ⁴F_3/2 and ⁴D_3/2 levels from the small variation of the distances R between Nd³⁺ ions in the pair is found. At least 2.7% variation of the value of the Nd-Nd distance R in the pair M-center was determined from the lifetime variation of the ⁴F_3/2 manifold with the assumption of a dipole-dipole interaction between the ions in the pair.The energy transfer up-conversion process responsible for the UV fluorescence observed when pumping the ⁴I_9/2(1)→⁴G_5/2(1) transition has been determined.     

Laser frequency stabilization at 1.5 microns using ultranarrow inhomogeneous absorption profiles in Er:LiYF4

Single-frequency diode lasers have been frequency stabilized to 1.5 kHz Allan deviation over 0.05-50 s integration times, with laser frequency drift reduced to less than 1.4 kHz/min, using the frequency reference provided by an ultranarrow inhomogeneously broadened Er³⁺:⁴I_15/2→⁴I_13/2 optical absorption transition at a vacuum wavelength of 1530.40 nm in a low-strain LiYF₄ crystal. The 130 MHz full-width at half-maximum (FWHM) inhomogeneous line width of this reference transition is the narrowest reported for a solid at 1.5 μm. Strain-induced inhomogeneous broadening was reduced by using the single isotope ⁷Li and by the very similar radii of Er³⁺ and the Y³⁺ ions for which it substitutes. To show the practicability of cryogen-free cooling, this laser stability was obtained with the reference crystal at 5 K; moreover, this performance did not require vibrational isolation of either the laser or crystal frequency reference. Stabilization is feasible up to T=25 K where the Er³⁺ absorption thermally broadens to ∼500 MHz. This stabilized laser system provides a tool for interferometry, high-resolution spectroscopy, real-time optical signal processing based on spatial spectral holography and accumulated photon echoes, secondary frequency standards, and other applications such as quantum information science requiring narrow-band light sources or coherent detection.     

Absorption and emission characteristics of Er3NbO7 phosphor: A comparison with ErNbO4 phosphor and Er:LiNbO3 single crystal

Er₃NbO₇ phosphor was synthesized by sintering a mixture of Er₂O₃ and Nb₂O₅ powder in a molar ratio of 3:1 at 1600 °C over 55 h. Optical absorption and emission characteristics of Er³⁺ ions in the calcined Er₃NbO₇ powder were investigated and discussed compared with ErNbO₄ phosphor and a Z-cut congruent Er (2 mol%):LiNbO₃ single crystal. The absorption and emission studies show that, due to different crystal structures, the spectroscopic properties of these niobates have some differences in spectral shape, peak position, and relative intensity, especially at 1.5 μm. The most obvious spectral feature of the Er₃NbO₇ is that the spectral structure of band instead of peak is observed in its absorption or emission spectrum due to the existence of local structural disorder and multiple Er³⁺ sites. The Er₃NbO₄ shows stronger upconversion emission than the single crystal but weaker than the ErNbO₄. Experimental results show that energy transfer upconversion and/or excited state absorption play a dominant role in the upconversion emissions, and, at higher pump level (>200 mW), the thermal effect becomes significant and results in drop of the upconversion intensity. The 1.5 μm lifetimes of Er³⁺ ion in the Er₃NbO₇, ErNbO₄ phosphor, and in the Er:LiNbO₃ crystal are measured to be ∼5.3, 2.0, and 2.4 ms, respectively. In combination with the measured Raman spectra, the quantum efficiency, multiphonon nonradiative decay rate, and theoretical radiative lifetime of the 1.5 μm emission of the two powder materials are expected. The differences in upconversion intensity and measured 1.5 μm lifetime between the three materials are explained qualitatively.     

Er3+，Tm3+共掺的NaY(WO4)2晶体的光谱分析和上转换发光

在室温下，测量了Er:Tm:NaY(WO₄)₂晶体的吸收光谱、激发光谱、发射光谱以及上转换发光，并运用J-O理论对测量的结果进行了计算，得出了Er:Tm:NaY(WO₄)₂晶体的强度参数.报道了Tm，Er离子间特殊的能量传递和相关上转换，解释了离子间的能级跃迁过程.同时，对于Er增强Tm离子近红外发光的特性也作了充分研究. 关键词： 4)₂晶体')" href="#">Er:Tm:NaY(WO₄)₂晶体 吸收光谱 发射光谱 激发光谱 上转换     

Crystalline-structure-dependent green and red upconversion emissions of Er-Yb-Li codoped TiO2

Crystalline structures and infrared-to-visible upconversion luminescence spectra have been investigated in 1 mol% Er³⁺, 10 mol% Yb³⁺ and 0-20 mol% Li⁺ codoped TiO₂ [1Er10Yb(0-20)Li:TiO₂] nanocrystals. The crystalline structures of 1Er10Yb(0-20)Li:TiO₂ were divided into three parts by the addition of Yb³⁺ and Li⁺. Both green and red upconversion emissions were observed from the ²H_11/2/⁴S_3/2 → ⁴I_15/2 and ⁴F_9/2 → ⁴I_15/2 transitions of Er³⁺ in Er³⁺-Yb³⁺-Li⁺ codoped TiO₂, respectively. The green and red upconversion emissions of 1Er:TiO₂ were enhanced significantly by Yb³⁺ and Li⁺ codoping, in which the intensities of green and red emissions and the intensity ratio of green to red emissions (I_green/I_red) were highly dependent on the crystalline structures. The significant enhanced upconversion emissions resulted from the energy migration between Er³⁺ and Yb³⁺ as well as the distortion of crystal field symmetry of Er³⁺ caused by the dissolving of Li⁺ at lower Li⁺ codoping concentration and the phase transformation at higher Li⁺ concentration. It is concluded that codoping with ions of smaller ionic radius like Li⁺ can efficiently improve the upconversion emissions of Er³⁺ or other rare-earth ions doped luminsecence materials.     

Growth and optical property of ZnWO4: Er crystal

Good quality crystals ZnWO₄ activated with Er³⁺ have been grown by means of Czochralski method and characterized using optical spectroscopy techniques. XRD, absorption spectra, fluorescence spectrum are presented and the Judd-Ofelt intensity parameters Ω₂, Ω₄, and Ω₆ are obtained to be 6.76×10^-20, 0.37×10^-20, and 0.50×10^-20 cm², respectively. Along crystallographic axes, refractive indices are presented. The fluorescence decay time of the ⁴I_13/2 level has also been investigated and shows an exponential behavior with a lifetime value of 5.52 ms. The crystal is potentially used for green and infrared eye-safe lasers.     

Improvement of Er:I11/2→Ce:F5/2 energy transfer rate in Er/Ce co-doped TeO2-ZnO-Na2O-Nb2O5 glasses

The B₂O₃ component was introduced into Er³⁺/Ce³⁺ co-doped TeO₂-ZnO-Na₂O-Nb₂O₅ glass to improve energy transfer rate of Er³⁺:⁴I_11/2→Ce³⁺:²F_5/2 phonon-assisted cross-relaxation process. With the 6 mol% substitution of B₂O₃ for TeO₂, the energy transfer rate increased from 1300 to 1831 s⁻¹ and the fluorescence intensity increased by about 13.4%. However, the more B₂O₃ substitution in the same glass system reduced the quantum efficiency of Er³⁺:⁴I_13/2→⁴I_15/2 transition due to the higher OH⁻ group concentration. The results show that an appropriate amount of B₂O₃ component can be used to improve the phonon-assisted energy transfer rate and enhance 1.53 μm fluorescence emission by increasing the phonon energy of host glass. The effect of B₂O₃ on the energy transfer process, the lifetimes of the ⁴I_11/2 and ⁴I_13/2 levels, and the upconversion emission have also been investigated.     

Synthesis and optical properties of KZnLa0.99Nd0.01(VO4)2 triple vanadate(V)—New promising laser materials

In an attempt to find a neodymium-vanadate system with long lifetime of ⁴F_3/2 level and relatively strong ⁴F_3/2→⁴I_11/2 emission for laser applications, the optical properties of Nd³⁺ in a new KZnLa(VO₄)₂ host is reported. The crystalline samples were obtained at 900 °C in air. The samples were crystallized in monoclinic system and were isostructural with KZnLa(PO₄)₂. KZnLa_0.99Nd_0.01(VO₄)₂ strongly emits in the near infrared range with the maxima at 871.6 and 1057 nm upon excitation through the ⁴F_5/2 level (808 nm) or by the charge transfer bands of VO₄³⁻. The lifetime of ⁴F_3/2 level of Nd³⁺ ion is larger than that observed in other neodymium-vanadates systems.     

Photoluminescence characteristics of energy transfer between Er and Bi in Gd2O3: Er, Bi

The phosphors, Bi³⁺- activated Gd₂O₃:Er³⁺, were prepared by sol-gel combustion method, and their photoluminescent properties were investigated under ultraviolet light excitation. The emission spectrum exhibited sharp peaks at about 520, 535, 545, 550 and 559 nm due to (²H_11/2, ⁴S_3/2)→⁴I_15/2 transitions of Er³⁺ ions. The luminescent intensity was remarkably improved by the incorporation of Bi³⁺ ions under 340 nm light excitation, which suggested very efficient energy transfer from Bi³⁺ ions to Er³⁺ions. The introducing of Bi³⁺ ions broadened the excitation band of the phosphor, of which a new strong peak occurred ranging from 320 to 360 nm due to the 6s²→6s6p transition of Bi³⁺ ions. There is significant energy overlap between the emission band of Bi³⁺ ions and the excitation band of Er³⁺ ions. Under 340 nm light excitation, Bi³⁺ absorbed most of the energy and transferred it to Er³⁺. The energy transfer probability from Bi³⁺ to Er³⁺ is strongly dependent on the Bi³⁺ ion concentration. Also, the sensitization effectiveness was studied and discussed in this paper.     

Optical properties of Er/Yb-codoped transparent PLZT ceramic

Optical absorption and emission spectra of Er³⁺/Yb³⁺ ions in PLZT (Pb_1−xLa_xZr_yTi_1−yO₃) ceramic have been studied. Based on the Judd—Ofelt (J-O) theory, the J-O intensity parameters were calculated to be Ω₂=2.021×10⁻²⁰ cm², Ω₄=0.423×10⁻²⁰ cm², Ω₆=0.051×10⁻²⁰ cm² from the absorption spectrum of Er³⁺/Yb³⁺-codoped PLZT. The J-O intensity parameters have been used to calculate the radiative lifetimes and the branching ratios for some excited ⁴I_13/2, ⁴I_11/2, ⁴I_9/2⁴F_9/2, and ⁴S_3/2 levels of Er³⁺ ion. The stimulated emission cross-section (8.24×10⁻²¹ cm²) was evaluated for the ⁴I_13/2→⁴I_15/2 transition of Er³⁺. The upconversion emissions at 538, 564, and 666 nm have been observed in Er³⁺/Yb³⁺-codoped PLZT by exciting at 980 nm, and their origins were identified and analyzed.