Spectroscopic and lasing properties of Er3+-doped glass microspheres

We report experimental results on the characterization of microspherical cavities fabricated in Er³⁺-doped modified-silica and phosphate glasses. The spectroscopic properties of the bulk precursor glasses as compared to the obtained microspheres were investigated by photoluminescence spectroscopy and lifetime measurement for the ⁴I_13/2 → ⁴I_15/2 transition of Er³⁺ ions. In both types of glasses we demonstrate whispering gallery mode laser action at various wavelengths around 1550 nm by using a 1480 nm pump laser coupled through a tapered fiber.     

Optical properties of Er3+-doped alkali fluorophosphate glasses

A systematic study of the optical absorption and luminescence spectra of Er³⁺-doped alkali fluorophosphate glasses (RTFP) 50(NaPO₃)–10TeO₂–20AlF₃–19RF–1Er₂O₃ (R = Li, Na and K) has been performed. The phenomenological Judd–Ofelt intensity parameters have been determined from the spectral intensities of the absorption bands in order to calculate the radiative transition probabilities, radiative lifetimes and branching ratios for various excited luminescent states. Using the visible and near infrared emission spectra, full width at half maximum (FWHM), emission cross-sections (σ_e) and figure of merit (FOM) were evaluated and compared with other hosts. Especially, the numerical values of these parameters indicate that the emission transition ⁴I_13/2 → ⁴I_15/2 transition at 1.534 μm in Er³⁺-doped fluorophosphate glasses may be highly useful in optical communication. The decay characteristic of ⁴S_3/2 excited level has also been recorded and analyzed. The calculated and experimental lifetimes were compared in terms of quantum efficiencies and multiphonon relaxation rates.     

Thermo-optical properties and nonradiative quantum efficiency of Er3+-doped and Er3+/Tm3+-co-doped tellurite glasses

Thermal lens (TL) measurements were performed in tellurite glasses, 70TeO₂–19WO₃–7Na₂O–4Nb₂O₅ (mol%), undoped, doped with Er³⁺ (1.19 × 10²⁰ ions/cm³) and co-doped with Er³⁺ (1.19 × 10²⁰ ions/cm³)/Tm³⁺ (1.56 × 10²⁰ ions/cm³). The absolute nonradiative quantum efficiency (ϕ) was determined by the TL method. The ϕ values for Er³⁺/Tm³⁺-co-doped and Er³⁺-doped tellurite glasses were 0.98 and 0.74, respectively. Fluorescence spectra were performed at λ_e = 488 nm and used to estimate the fluorescence quantum efficiency (η) using the TL results. These values were compared with results obtained by Judd–Ofelt calculations.     

Er3+掺杂钨酸铅晶体的发光和光谱特征

本试验测试了Er3 掺杂钨酸铅晶体(PbWO4:Er3 )的吸收光谱,依据J-O理论,首次计算报道了光谱项特征:J-O强度参数、量子荧光效率、荧光分支比等,Ω2=3.75×10-20cm2,Ω4=0.67×10-20cm2,Ω6=0.41×10-20cm2。计算证实,PWO:Er3 中几乎有80%的激发能量非辐射跃迁转移致4I13/2能级,4I13/2的计算寿命是5200μs,J-O计算显示,在PWO中产生4I13/2→4I15/2和发射1.53μm.有高的几率。讨论了不同浓度Er3 掺杂对于吸收系数和PbWO4晶体光学吸收边的影响,讨论了Er3 掺杂PbWO4晶体的光致发光和X射线激发发光光谱,PbWO4:Er3 晶体中存在着从PbWO4基质到Er3 离子的能量传递,发光光谱的分析表明,这种能量传递是共振能量传递。     

Fabrication and characterization of Er3+-doped GeO2–PbO and GeO2–PbO–Bi2O3 glass fibers

Glass fibers were drawn from GeO₂–PbO–Bi₂O₃ and GeO₂–PbO melts previously doped with Er³⁺. From the differential thermal analysis curve, the glass transition temperature was determined to be 420 °C, and no crystallization peak was observed in the temperature range of that analysis, indicating stability with regard to devitrification. Raman spectroscopy was performed to characterize the structure of the glasses, which exhibited large transmission windows (0.5–5.0 μm) and large refractive indices (∼2.0). Infrared to visible upconversion of Er³⁺ was observed in the fibers. The visible emissions were related to the upconverted green emissions at about 530 nm (²H_11/2 → ⁴I_15/2) and 550 nm (⁴S_3/2 → ⁴I_15/2), and red emission at 668 nm (⁴F_9/2 → ⁴I_15/2) under 980 nm excitation. The infrared transition (⁴I_13/2 → ⁴I_15/2) was peaked at 1.53 μm. The results obtained suggest that the fibers exhibit the same structures as the parent glasses and can be used in upconversion fiber optical devices.     

Energy transfer and frequency upconversion in Pr3+-doped ZBLAN glass

The lifetimes of ³P₀ and ¹D₂ levels of Pr³⁺ were measured in ZBLAN glasses of composition in mol% 53ZrF₄–20BaF₂–(4 − x)LaF₃–3AlF₃–20NaF–xPrF₃ (x = 0.1, 0.5, 1, and 3) by resonant excitation. Energy transfer observed between Pr³⁺ ions was analyzed by means of the Inokuti–Hirayama theory. The non-exponential dependence of the ¹D₂ decay on Pr³⁺ concentration indicates that dipole–dipole interaction between Pr³⁺ is the main process. Orange-to-blue upconversion luminescence was observed and described by two-ion energy transfer mechanism. The temporal evolution of upconversion luminescence was characterized by rise and decay times related to the dopant concentration.     

Laser transition characteristics of Nd3+-doped fluorophosphate laser glasses

Fluorophosphate glasses of composition P₂O₅–K₂O–MgO–Al₂O₃–AlF₃ and P₂O₅–K₂O–MgO–Al₂O₃–BaF₂ were prepared with different Nd³⁺ ion concentrations. The absorption and emission spectra in the UV–VIS–NIR region were measured for these glasses. Judd–Ofelt analysis has been carried out using the absorption spectra of 1.0 mol% Nd³⁺-doped glasses to evaluate the radiative properties for some luminescent levels of the Nd³⁺ ion. The stimulated emission cross-sections of the ⁴F_3/2 → ⁴I_11/2 laser transition for the present glasses are found to be higher than for other Nd³⁺-doped glasses. Branching ratio calculations also revealed the potentiality of the ⁴F_3/2 → ⁴I_11/2 transition for laser action in these glasses. The observed concentration quenching of the lifetime of the ⁴F_3/2 level is explained as a result of cross-relaxation process between the Nd³⁺ ions.     

UV assisted local crystallization in Er3+ doped oxy-fluoride glass

We report on fabrication of Er³⁺-activated LaF₃ nanocrystals in transparent glasses using an original technique, which combines both heat treatment, below glass crystallization temperature, and ultraviolet laser irradiation at 244 nm. The main advantage of this method is to control the spatial localization of the nanoparticles in the glass sample, whereas annealing solely at the crystallization temperature leads to a fully crystallized glass sample. Thermal differential analysis was used to determine the crystallization temperature of the sample. The photoluminescence spectra behaviour of Er³⁺ ions, collected from the UV-irradiated and unirradiated regions, allowed us to follow and to distinguish the structural changes in the glass network under heat treatment and ultraviolet exposure.     

Fabrication and photoluminescence characteristics of Er3+-doped optical fiber sensitized by Si particles

We report for the first time the development of Er³⁺/Si-doped optical fiber amplifier operating at 1550 nm upon 512 nm pumping. Er³⁺-doped silica glass optical fibers incorporated with silicon particles as the sensitizer were fabricated by the modified chemical vapor deposition and the solution doping technique. The effect of silicon incorporation into the fiber core on the optical absorption and photoluminescence properties was investigated. Upon pumping with the CW Ar-ion laser at 512 nm, a photoluminescence band appeared near 770 nm and 1560 nm. The peak intensity of the photoluminescence at 1560 nm in the Er³⁺/Si-doped fiber was found to enhance by about 70% compared to the Er³⁺-doped fiber.     

1.5 μm Emission and infrared-to-visible frequency upconversion in Er+3/Yb+3-doped phosphoniobate glasses

Sodium phosphoniobate glasses with the composition (mol%) 75NaPO₃–25Nb₂O₅ and containing 2 mol% Yb³⁺ and x mol% Er³⁺ (0.01 ⩽ x ⩽ 2) were prepared using the conventional melting/casting process. Er³⁺ emission at 1.5 μm and infrared-to-visible upconversion emission, upon excitation at 976 nm, are evaluated as a function of the Er³⁺ concentration. For the lowest Er³⁺ content, 1.5 μm emission quantum efficiency was 90%. Increasing the Er³⁺ concentration up to 2 mol%, the emission quantum efficiency was observed to decrease to 37% due to concentration quenching. The green and red upconversion emission intensity ratio was studied as a function of Yb³⁺ co-doping and the Er³⁺–Er³⁺ energy transfer processes.     

Stimulated emission of Co2+-doped glass–ceramics

Pump–probe spectroscopy studies on cobalt-doped spinel-based aluminosilicate glass–ceramics of various compositions have been made in the visible part of the spectrum. Stimulated emission from the ⁴T₁(⁴P) state to the ⁴A₂ one of tetrahedral Co²⁺ ion has been observed for all glass–ceramic materials. The peak values of effective stimulated emission cross-sections for Co²⁺ ions are estimated to be 4–5 × 10⁻¹⁹ cm² depending on glass–ceramics composition and are found to be higher than in spinel single crystals.     

Upconversion and concentration quenching in Er3+-doped TeO2–Na2O binary glasses

The spectroscopic properties of Er³⁺-doped alkali tellurite TeO₂–Na₂O glasses are investigated. Infrared-to-visible upconversion emission bands are observed at 410, 525, 550 and 658 nm using 797 nm excitation wavelength. These bands are assigned to the ²H_9/2 → ⁴I_15/2, ²H_11/2 → ⁴I_15/2, ⁴S_3/2 → ⁴I_15/2 and ⁴F_9/2 → ⁴I_15/2 transition, respectively. The power dependence study reveals that the ²H_9/2 → ⁴I_15/2 transition involves a three-step process while the other upconversion transitions involve only two steps. An excitation with 532 nm wavelength, two upconversion bands are observed in the UV region at 380 and 404 nm in addition to bands in the visible region at 410, 475, 525, 550, 658 and 843 nm. These bands are ascribed to ⁴G_11/2 → ⁴I_15/2, ²P_3/2 → ⁴I_13/2, ²H_9/2 → ⁴I_15/2, ²P_3/2 → ⁴I_11/2, ²H_11/2 → ⁴I_15/2, ⁴S_3/2 → ⁴I_15/2, ⁴F_9/2 → ⁴I_15/2 and ⁴S_3/2 → ⁴I_13/2 transition, respectively. Increasing Er³⁺ concentration leads to a rapid growth in the intensity of red emission relative to that for the green emission. An explanation for this observation has been suggested. The temperature dependence profile for the two thermally coupled levels (²H_11/2, ⁴S_3/2) shows that they can be used for measuring the temperature.     

Effect of heat treatment on Er3+ containing multicomponent oxyfluoride lead borate glass system

Effect of heat treatment on Er³⁺ containing multicomponent oxyfluoride lead borate glasses in (72 ? x)PbO–xPbF₂–18B₂O₃–6Al₂O₃–3WO₃–1ErF₃ (where x = 9 or 72) system have been studied. The samples with low and high PbF₂ concentrations were analyzed using X-ray diffraction and luminescence spectroscopy. Several narrowed and relatively intense diffraction lines have been formed after heat treatment attributed to the orthorhombic PbF₂ phase. Luminescence spectroscopy revealed bands due to ⁴I_13/2–⁴I_15/2 and ⁴S_3/2–⁴I_15/2 transitions of Er³⁺ ions. This observation makes these glasses candidates for NIR laser active media and up-conversion applications.     

Photoluminescence of Sm3+, Dy3+, and Tm3+-doped transparent glass ceramics containing CaF2 nanocrystals

Photoluminescence properties of Sm³⁺, Dy³⁺, and Tm³⁺-doped transparent oxyfluoride silicate glass ceramics containing CaF₂ nanocrystals were reported. Emission bands of ⁴G_5/2 → ⁶H_5/2 (562 nm), ⁴G_5/2 → ⁶H_7/2 (598 nm), ⁴G_5/2 → ⁶H_9/2 (645 nm) and ⁴G_5/2 → ⁶H_11/2 (706 nm) for the Sm³⁺: glass and glass ceramic, with an excitation at ⁶H_5/2 → ⁴F_7/2 (402 nm) have been recorded. Of them, ⁴G_5/2 → ⁶H_7/2 (598 nm) has shown a bright orange emission. With regard to the Dy³⁺: glass, a bright fluorescent yellow emission at 575 nm (⁴F_9/2 → ⁶H_13/2) and blue emission at 481 nm (⁴F_9/2 → ⁶H_15/2) have been observed, apart from 662 nm (⁴F_9/2 → ⁶H_11/2) emission transition with an excitation at 386 nm (⁶H_15/2 → ⁴I_13/2 + ⁴F_7/2) wavelength. Emission bands of ¹G₄ → ³F₄ (650 nm) and ¹G₄ → ³H₅ (795 nm) transitions for the Tm³⁺: glass and glass ceramic, with an excitation at ³H₆ → ¹G₄ (467 nm) have been observed. Of them, ¹G₄ → ³F₄ (650 nm) has shown bright red emission. Decay lifetime measurements were also carried out for all the observed Sm³⁺, Dy³⁺, and Tm³⁺-doped glass and glass ceramic emission bands.     

Multiple sites for Er3+ in alkali silicate glasses (II). Evidence of four sites for Er3+

The low-temperature absorption spectrum of a series of binary alkali silicate glasses doped with Er³⁺ shows the presence of four different sites for the Er³⁺. The near-octahedral A site reported in Part I of this series is the principal site and is present in all these glasses. The B site appears in the binary lithium and sodium silicate glasses. The binary potassium, rubidium and cesium glasses show the presence of the C and D sites. The C site absorption spectrum is similar to that found by Gruber et al. for Er³⁺ in Er₂O₃. The D site is probably a variation of the B site. Tentative sixfold-coordinated models are suggested for the B and D sites.     

Fabrication of Er doped oxyfluoride-silicate glass film by pulsed laser deposition for planar amplifier

Pulsed laser deposition (PLD) technique has been employed to fabricate glassy films based on the Er³⁺ doped oxyfluoride lead-silicate glasses. Glassy films have been produced at temperatures between 300 and 400 °C with O₂ pressures ranging from 25 to 175 mTorr. The film microstructure appears to be determined mainly by substrate temperature. The film refractive index increases with higher temperatures and lower O₂ pressures. The photoluminescence intensity of Er³⁺ ions and lifetime are very much dependent on the film microstructure and defects. Fewer fabrication defects and less porous films produce stronger fluorescence intensity and longer lifetime of Er³⁺ ions. At an optimized temperature and O₂ pressure, the Er photoluminescence properties of the film can be reproduced and are very close to those of target glass. Consequently the work reported here suggested a good candidate for further investigation as a thin film material for EDWA.     

Development of chalcogenide glass photoresists for gray scale lithography

Wet and dry negative etching procedures are evaluated for the fabrication of 3D graded microstructures in As–S based inorganic photoresists. Absorption of light and consequent photostructural changes near the surface layer enhance the chemical resistance of the As–S films. The success of the procedure is demonstrated by fabricating arrays of 12 μm diameter microlenses in a thin As₃₅S₆₅ film using a gray scale Cr mask and wet etching. The selectivity of dry etching is successfully realized by using photodiffusion in Ag–As₂S₃ bilayer structure. In this case, however, surface roughness or ‘grass’ is observed after etching. An unexpected segregation of silver is observed at the edges and at the boundary between the exposed and unexposed regions, which is investigated by SEM and XPS.     

铒镱双掺的钒酸钇和铌酸锂晶体中的铒离子的上转换发光

利用J-O理论,计算了在铒、镱双掺的钒酸钇和铌酸锂晶体中的铒离子在室温下的晶场唯象参数Ωλ(λ=2,4,6)及辐射跃迁几率、无辐射跃迁几率和共振跃迁几率.考虑到铒、镱间的能量转移,写出了在这些晶体中的铒离子的速率方程.速率方程的解表明,在铒、镱双掺的钒酸钇晶体中的铒离子的550 nm的上转换发光,比它在铒、镱双掺的铌酸锂晶体中更为有效.这一理论结果与我们的实验观察结果一致.