2–3 μm emission and fluorescent decaying behavior in Ho3+-doped tellurium germanate glass

In this work, we report the 2.05 μm emission and ∼3 μm broadband spectra of Ho₂O₃-doped 33GeO₂–30TeO₂–27PbO–10CaO (in mol%) glass under 640 nm laser excitation. Clear emission spectra due to the ⁵I₇–⁵I₈ transition and the ⁵I₆–⁵I₇ transition in Ho³⁺ are observed. The 2.05 μm emission intensity and the full width at half maximum (FWHM) of the ∼3 μm broadband depend on the Ho concentration. The peak stimulated emission cross-section of Ho³⁺ is 6.57 × 10⁻²¹ cm² at 2.05 μm, as calculated by the McCumber theory. The emission spectra are recorded and the maximum emission intensity at 2.05 μm is obtained at a doping level of 0.5 mol% Ho₂O₃ in the glass. A broad and flat emission band from 2700 nm to 3050 nm is observed in 2 mol% Ho₂O₃-doped tellurium germanate glass. The lifetime of the ⁵I₇ state decreases with the increase in Ho³⁺ concentration due to non-radiative relaxation processes. An energy transfer coefficient of 271.88 mol⁻¹ s⁻¹ is obtained.     

Improving 1.54 μm emission by inducting Ti ion in Er3+/Yb3+ codoped phosphate glass ceramic

Er³⁺/Yb³⁺ doped phosphate glasses were prepared by high-temperature melting method. Under 975 nm excitation, the intensity of the visible light in the sample doped with TiO₂ is weaker compared to that of the sample un-doped with TiO₂ However, the intensity of the 1540 nm emission in the sample doped with TiO₂ is stronger than that in the sample un-doped with TiO₂ The sample can efficiently improve the 1540 nm emission by absorbing visible light.     

Enhanced emission of 2.7 μm from Er3+/Nd3+-codoped LiYF4 single crystals

An Er³⁺/Nd³⁺ co-doped LiYF₄ single crystal of ～Φ 12 mm × 95 mm size with high quality was grown by a Bridgman method. The luminescent properties of the crystals with different Er³⁺ and Nd³⁺ concentrations were studied. Compared with the Er³⁺ single-doped LiYF₄ crystal extremely enhanced emission at 2.7 μm from the Er³⁺/Nd³⁺ co-doped LiYF₄ was observed upon excitation of an 800 nm laser diode. Meanwhile, the green up-conversion emission and near infrared emission at 1.5 μm from Er³⁺ in the co-doped crystals were effectively restricted. The luminescent mechanisms for the Er³⁺/Nd³⁺ co-doped crystals were analyzed and the possible energy transfer processes were proposed. The energy transfer efficiencies for (Er³⁺:⁴I_13/2, Nd³⁺:⁴I_9/2) → (Er³⁺:⁴I_15/2, Nd³⁺:⁴I_15/2) and (Nd³⁺:⁴F_3/2, Er³⁺:⁴I_15/2) → (Nd³⁺:⁴I_9/2, Er³⁺:⁴I_9/2) were calculated. It was found that Er³⁺/Nd³⁺ co-doped single crystal may be a potential host for 2.7 μm lasers.     

Spectral properties of Ho3+/Tm3+ co-doped β′-Gd2(MoO4)3 crystal as laser gain medium around 2.0 μm

Ho³⁺/Tm³⁺ co-doped β′-Gd₂(MoO₄)₃ single crystal was investigated as gain medium for Ho³⁺ laser around 2.0 μm. Polarized absorption and fluorescence spectra of the crystal were measured. Polarized spectral parameters of Ho³⁺ ions in the crystal were calculated and the gain curves around 2.0 μm were estimated. The fluorescence decay curves for Tm³⁺ and Ho³⁺ ions related to the 2.0 μm laser were measured and analyzed. The distinct coupled decay behavior for the Ho³⁺/Tm³⁺ co-doped system embodies the existence of energy transfer between Tm³⁺ and Ho³⁺ ions.     

Spectroscopic properties of Tm3+/Al3+ co-doped sol–gel silica glass

Tm³⁺/Al³⁺ co-doped silica glass was prepared by sol–gel method combined with high temperature sintering. Glasses with compositions of xTm₂O₃–15xAl₂O₃–(100 − 16x) SiO₂ (in mol%, x = 0.1, 0.3, 0.5, 0.8 and 1.0) were prepared. The high thulium doped silica glass was realized. Their spectroscopic parameters were calculated and analyzed by Judd–Ofelt theory. Large absorption cross section (4.65 × 10⁻²¹ cm² at 1668 nm) and stimulated emission cross section (6.00 × 10⁻²¹ cm² at 1812 nm), as well as low hydroxyl content (0.180 cm⁻¹), long fluorescence lifetime (834 μs at 1800 nm), large σ_em × τ_rad (30.05 × 10⁻²¹ cm² ms) and large relative intensity ratio of the 1.8 μm (³F₄ → ³H₆) to 1.46 (³H₄ → ³F₄) emissions (90.33) are achieved in this Tm³⁺/Al³⁺ co-doped silica glasses. According to emission characteristics, the optimum thulium doping concentration is around 0.8 mol%. The cross relaxation (CR) between ground and excited states of Tm³⁺ ions was used to explain the optimum thulium doping concentration. These results suggest that the sol–gel method is an effective way to prepare Tm³⁺ doped silica glass with high Tm³⁺ doping and prospective spectroscopic properties.     

Luminescence at 1.53 μm for a new Er3+-doped transparent oxyfluoride glass ceramic

Transparent 45SiO₂25Al₂O₃5CaO10NaF15CaF₂ glass ceramics doped with different levels of Er³⁺ were prepared. The spherical CaF₂ nanocrystals with 10–20 nm in size were verified to be homogeneously embedded among the glassy matrix. Room temperature absorption and emission spectra corresponding to ⁴I_13/2 ↔ ⁴I_15/2 transitions of Er³⁺ ions in precursor glasses and glass ceramics, respectively had been measured. For glass ceramics, with increasing of Er³⁺ content from 0.1 to 2.0 mol%, the FWHM values of the emission bands increased from 42 to 71 nm; meanwhile, the lifetime of ⁴I_13/2 level slightly reduced. However, both the values of FWHM and lifetime were larger than those of precursor glasses due to the change of ligand field of Er³⁺ ions.     

Luminescence quantum efficiency at 1.5 μm of Er3+-doped tellurite glass determined by thermal lens spectroscopy

Erbium doped tellurite glasses (TeO₂ + Li₂O + TiO₂) were prepared by conventional melt-quenching method to study the influence of the Er³⁺ concentration on the luminescence quantum efficiency (η) at 1.5 μm. Absorption and luminescence data were used to characterize the samples, and the η parameter was measured using the well-known thermal lens spectroscopy. For low Er³⁺ concentration, the measured values are around 76%, and the concentration behavior of η shows Er–Er and Er–OH⁻ interactions, which agreed with the measured lifetime values.     

Effective improvement of 2.0-µm and 4.1-µm mid-infrared emission in Tm3+/Ho3+-co-doped tellurite glasses

Journal of Materials Science: Materials in Electronics - Tm3+/Ho3+-co-doped tellurite glasses were fabricated by employing the high-temperature melting technology to achieve intense mid-infrared...     

Structure and optical properties of Dy3+/Tm3+ co-doped oxyfluoride glass ceramics containing β-NaGdF4 nanocrystals

Dy³⁺/Tm³⁺ co-doped oxyfluoride glass ceramics containing hexagonal β-NaGdF₄ nanocrystals were prepared by the melt-quenching method and subsequent heat-treatment procedure. During the crystallization process, the structural evolution of glass network was systematically investigated using XRD, TEM and FTIR spectra. Experimental results provided new evidences that a silica-enriched layer around the precipitated fluoride nanocrystals was formed during the crystallization process. Strong white light emission was obtained in the oxyfluoride glass ceramics by modifying the relative concentration ratio of Tm³⁺ and Dy³⁺ ions.     

The 1.53 μm spectroscopic properties of Er3+/Ce3+/Yb3+ tri-doped tellurite glasses containing silver nanoparticles

The metallic silver nanoparticles (NPs) was introduced into the Er³⁺/Ce³⁺/Yb³⁺ tri-doped tellurite glasses with composition TeO₂–ZnO–La₂O₃ to improve the 1.53 μm band fluorescence. The UV/Vis/NIR absorption spectra, 1.53 μm band fluorescence spectra, fluorescence lifetimes, X-ray diffraction (XRD) curves, differential scanning calorimeter (DSC) curves and transmission electron microscopy (TEM) image of tri-doped tellurite glasses were measured, together with the Judd–Ofelt intensity parameters, emission cross-sections, absorption cross-sections and radiative quantum efficiencies were calculated to investigate the effects of silver NPs on the 1.53 μm band spectroscopic properties of Er³⁺ ions, structural nature and thermal stability of glass hosts. It is shown that Er³⁺/Ce³⁺/Yb³⁺ tri-doped tellurite glasses can emit intense 1.53 μm band fluorescence through the combined energy transfer (ET) processes from Yb³⁺ to Er³⁺ ions and Er³⁺ to Ce³⁺ ions under the 980 nm excitation. At the same time, the introduction of an appropriate amount of silver NPs can further improve the 1.53 μm band fluorescence owing to the enhanced local electric field effect induced by localized surface Plasmon resonance (LSPR) of silver NPs and the possible energy transfer from silver NPs to Er³⁺ ions, and an improvement by about 120% of fluorescence intensity is found in the studied Er³⁺/Ce³⁺/Yb³⁺ tri-doped tellurite glass containing 0.5 mol% amount of silver NPs with average diameter of ∼15 nm. The energy transfer mechanisms from Yb³⁺ to Er³⁺ ions and Er³⁺ to Ce³⁺ ions were also quantitatively investigated by calculating energy transfer microparameters and phonon contribution ratios. Furthermore, the thermal stability of glass host increases slightly with the introduction of silver NPs while the glass structure maintains the amorphous nature. The results indicate that the prepared Er³⁺/Ce³⁺/Yb³⁺ tri-doped tellurite glass with an appropriate amount of silver NPs is an excellent gain medium applied for 1.53 μm band EDFA pumped with a 980 nm laser diode (LD).     

Polarized spectral properties and 1.5–1.6 μm laser operation of Er:Sr3Yb2(BO3)4 crystal

Undoped and Er³⁺-doped Sr₃Yb₂(BO₃)₄ crystals were grown by the Czochralski method. Room temperature polarized spectral properties of the Er:Sr₃Yb₂(BO₃)₄ crystal were investigated. The efficiency of the energy transfer from Yb³⁺ to Er³⁺ ions in this crystal was calculated to be about 95%. End-pumped by a diode laser at 970 nm in a hemispherical cavity, a 0.75 W quasi-CW laser at 1.5–1.6 μm with a slope efficiency of 7% and an absorbed pump threshold of 3.8 W was achieved in a 0.5-mm-thick Z-cut crystal glued on a 5-mm-thick pure YAG crystal with UV-curable adhesive.     

Luminescence at 2.8 μm: Er3+-doped chalcogenide micro-waveguide

This paper reports the fabrication of luminescent optical rib/ridge waveguides made of erbium doped Ga-Ge-Sb-S films deposited by RF magnetron sputtering. Several fluorescence emissions of Er³⁺ ions from the visible to the middle infrared spectral domain were clearly observed within the films. The study of the ⁴I_13/2 level lifetime enabled development of a suitable annealing treatment of the films to reach the value of the bulk counterpart while the variation in surface roughness was limited, thus ensuring reasonable optical losses (0.7–0.9 dB/cm). Amplification experiments were carried out at 1.54 μm leading to complete characterization of the erbium-doped micro-waveguide with ∼3.4 dB/cm on/off gain. A demonstration of mid-IR photoluminescence from Er³⁺-doped chalcogenide micro-waveguide was recorded at ∼2.76 μm. The multi-luminescence from the visible to mid-IR generated using erbium doped chalcogenide waveguiding micro-structures might find easy-to-use applications concerning telecommunication technologies or on-chip optical sensors for which luminescent sources or amplifiers operating at different wavelengths are required.     

Spectroscopic properties and energy transfer in Er–Tm co-doped bismuth silicate glass

In this paper, we investigate the spectroscopic properties of and energy transfer processes in Er–Tm co-doped bismuth silicate glass. The Judd–Ofelt parameters of Er³⁺ and Tm³⁺ are calculated, and the similar values indicate that the local environments of these two kinds of rare earth ions are almost the same. When the samples are pumped at 980 nm, the emission intensity ratio of Tm:³F₄ → ³H₆ to Er:⁴I_13/2 → ⁴I_15/2 increases with increased Er³⁺ and Tm³⁺ contents, indicating energy transfer from Er:⁴I_13/2 to Tm:³F₄. When the samples are pumped at 800 nm, the emission intensity ratio of Er:⁴I_13/2 → ⁴I_15/2 to Tm:³H₄ → ³F₄ increases with increased Tm₂O₃ concentration, indicating energy transfer from Tm:³H₄ to Er:⁴I_13/2. The rate equations are given to explain the variations. The microscopic and macroscopic energy transfer parameters are calculated, and the values of energy transfer from Er:⁴I_13/2 to Tm:³F₄ are found to be higher than those of the other processes. For the Tm singly-doped glass pumped at 800 nm and Er–Tm co-doped glass pumped at 980 nm, the pumping rate needed to realize population reversion is calculated. The result shows that when the Er₂O₃ doping level is high, pumping the co-doped glass by a 980 nm laser is an effective way of obtaining a low-threshold ∼2 μm gain.     

Environment segregation of Er3+ emission in bulk sol–gel-derived SiO2–SnO2 glass ceramics

Er-doped (100-x) SiO₂–x SnO₂ glass–ceramic monoliths were prepared using a sol–gel method. Raman spectroscopic measurements showed the structural evolution of the silica matrix caused by the formation and the growth of SnO₂ nanocrystals. Analysis of the photoluminescence properties shows that the quantity of Er³⁺ ions embedded in the vicinity of SnO₂ nanocrystals could be controlled by the SnO₂ concentration. We give spectroscopic evidence of energy transfer to erbium ions provided by SnO₂ nanocrystals in the silica matrix. The ⁴I_13/2 level decay curves present a double-exponential profile with two lifetimes associated to rare-earth ions in two different environments.     

Tailoring the 4I9/2 → 4I13/2 emission in Er3+ ions in different hosts media

The ⁴I_9/2–⁴I_13/2 emission band of Er³⁺ is potentially interesting for CH₄ detection because it can overlap with the optical absorption band of CH₄. GaLaS and GeGaS glasses doped with Er³⁺ ions show the desirable emission under 808 nm excitation. An attempt of spectrally shifting ⁴I_9/2–⁴I_13/2 emission band by substituting S by O or Se to obtain a perfect match to the absorption band of CH₄ leads to the weakening and disappearance of the ⁴I_9/2–⁴I_13/2 band. This phenomenon is tentatively related to the acceleration of non-radiative relaxation in the case of oxygen addition and to the suppression of up-conversion in the selenium substitution case. The relative intensity of the ⁴I_9/2–⁴I_13/2 band (with respect to the ⁴I_13/2–⁴I_15/2 band) varies significantly in powdered and bulk materials. This effect is discussed in terms of the radiation diffusion (i.e. radiation trapping) model and is confirmed by Monte-Carlo simulations.     

Manipulation and welding of metal spheres above 10 μm using needle-like probe

A needle-like probe is the simplest tool to manipulate fine spheres. It catches fine spheres by adhesion forces without any holding device. Metallic spheres of 10–100 μm are difficult to manipulate with the needle-like probe, because the gravity rivals the adhesion forces in the dynamics of the spheres. Large and heavy spheres arranged on a substrate are easily disturbed because of the same reason. Here, a manipulator equipped with a direct power source, which applies voltage to the probe, is fabricated. Large and heavy spheres are adhered by the controllable electrostatic force. Besides the manipulation, the apparatus is designed to weld the spheres by using the probe as electrode for spot/arc welding. Experiments on the manipulation showed that the probe caught gold spheres of 40–80 μm by applying 20–50 V and released by putting them down after cutting the power off. Following to manipulation, welding experiments were carried out at various conditions. Two power sources, a high-voltage and low-current power source and a low-voltage and high-current power source, and two welding methods, arc welding and spot welding, are examined. The experiments showed that the gold spheres of 40–80 μm can be welded by the spot welding using the high-voltage and low-current power source, of which maximum power rating is 10 kV×1 mA. The probe is kept to touch the sphere and 4 kV or more is applied. Electric sparks are generated at the interface of the probe and the substrate, and the sphere is welded to the substrate. In both the manipulation and welding, the contact pressure must be very low. A tower of gold spheres is fabricated as an example of three-dimensional microstructures composed of fine spheres.     

Polarized spectroscopic properties of Ho-doped LuLiF4 single crystal for 2 μm and 2.9 μm lasers

Polarized spectroscopic properties of a Ho³⁺-doped LuLiF₄ (Ho:LuLF) single crystal grown by the Czochralski method have been investigated as a promising material for 2 μm and 2.9 μm lasers. The Judd-Ofelt (J-O) model has been applied to the analysis of the polarized room temperature absorption spectra to establish the so-called J-O intensity parameters. Based on the calculated parameters, we determined the emission probabilities, branching ratio and radiative lifetime for the Ho³⁺ transitions from the excited state manifolds to the lower-lying manifolds. Ho:LuLF crystal shows long fluorescence lifetime of ⁵I₇ manifold (16 ms) and broad absorption and emission spectra, which exhibit strong polarization characteristics. Stimulated emission cross-sections spectra of the ⁵I₆ → ⁵I₇ and ⁵I₇ → ⁵I₈ transitions were derived and compared with those of the other well-known Ho³⁺-doped laser crystals.     

Structural and luminescent properties of Er3+ and Tb3+-doped sol–gel-based bioactive glass powders and electrospun nanofibers

In this study, sol–gel-based erbium (Er³⁺), terbium (Tb³⁺) and Er³⁺: Tb³ co-doped 1393 bioactive glass powders and electrospun nanofibers were prepared. Structural and morphological properties of the bioactive glasses as well as the photoluminescence characteristics were investigated in detail. The median particle size and average diameter of the prepared glass powders and fibers were in the range of ~ 1.5–3.5 μm and 280–660 nm, respectively. The steady-state photoluminescence and decay kinetics of the samples were investigated under excitation (374 nm) where only Er³⁺ and Tb³⁺ ions close to Si nanoclusters can be excited. All the samples prepared in the study exhibited bright green emission upon excitation at 374 nm. Results showed that the dopant concentration and the sample morphology have significant influence on the photoluminescence and decay properties of the glasses. Sol–gel-derived bioactive glass particles exhibited stronger emission intensity, whereas electrospun nanofibers showed extended decay times. In vitro bioactivity experiments revealed that Er³⁺ and Tb³⁺ doping did not inhibit the conversion of the glass samples to hydroxyapatite treated in simulated body fluid for 30 days. It was concluded that Er³⁺ and Tb³⁺-containing 1393 bioactive glasses have a potential to be used in tissue engineering applications as well as bioimaging studies.

     

Dy3+ doped GeGaSbS fluorescent fiber at 4.4 μm for optical gas sensing: Comparison of simulation and experiment

The infrared (IR) fluorescence from Dy³⁺ doped Ga₅Ge₂₀Sb₁₀S₆₅ fibers is investigated in details in order to develop bright IR fiber sources emitting at 4.4 μm for CO₂ sensing purposes. Optical sensing requires intense IR radiation to probe with accuracy gas concentrations by measuring the gas absorption. We developed a specific modeling describing the Dy³⁺ doped GeGaSbS fiber IR output power by simultaneously solving rate equations and propagation equations within the fibers. This modeling allows the determination of the IR fluorescence guided along the fiber as a function of the Dy³⁺ doping concentration, the propagation losses and the fiber geometry. The results of the simulation are successfully compared with experimental data and are further discussed in order to determine the optimal set of fiber characteristics maximizing the IR fiber output emission.