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.     

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.     

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.     

Upconversion luminescence of Er/Yb-codoped natrium-germanium-bismuth glasses

The absorption and upconversion fluorescence spectra of a series of Er³⁺/Yb³⁺-codoped natrium-germanium-bismuth glasses have been studied. The transition probabilities, excited state lifetimes, and the branching ratios have been predicted for Er³⁺ based on the Judd-Ofelt theory. At room temperature, an upconversion efficiency of 6.1×10⁻² has been obtained for the green emission from the glass with 0.5 wt% Er₂O₃ and 3.0 wt% Yb₂O₃ pumped by 980 nm radiation with an intensity of 270 W/cm². And the “standardized” efficiency for green upconversion light is higher than that reported in lead-germanate, lead-tellurite-germanate, and silicate glasses. The results indicate that the Er³⁺/Yb³⁺-codoped natrium-germanium-bismuth oxide glass may be a potential material for developing upconversion optic devices.     

Optical spectroscopy of Er:YSGG laser crystal

Er:YSGG single crystals with good optical quality were grown by Czochralski method. X-ray diffraction (XRD) measurements show that the crystal lattice parameters of the 30 at.% Er³⁺-doped YSGG crystal were a=b=c=12.4640±0.0065 Å, α=β=γ=90°. The doping concentration of Er³⁺ in YSGG was calculated. The absorption spectrum and photoluminescence spectra of Er:YSGG crystal were studied at room temperature. Based on Judd-Ofelt (J-O) theory, the J-O intensity parameters Ω_t (t=2, 4, 6), the experimental and theoretical oscillator strengths were calculated using the absorption spectrum. The intensity parameters Ω_t (t=2,4,6) obtained to be Ω₂=0.23×10⁻²⁰ cm², Ω₄=0.86×10⁻²⁰ cm², Ω₆=0.37×10⁻²⁰ cm², respectively. With these intensity parameters, the line strengths, oscillator strengths, transition probabilities, fluorescence branching ratios and radiation lifetimes were calculated. The photoluminescence spectra and excitation spectrum of Er:YSGG were measured and studied.     

Growth and spectroscopic characterization of Er: Sr3Y(BO3)3 crystal

This paper reports the growth and spectroscopic characterization of Er³⁺:Sr₃Y(BO₃)₃ crystal. Er³⁺:Sr₃Y(BO₃)₃ crystal with dimensions up to ∅20×35 mm³ has been grown by Czochralski method. The polarized spectroscopic properties of Er³⁺:Sr₃Y(BO₃)₃ crystal were investigated. Based on the Judd-Ofelt theory, the effective intensity parameters Ω_t were obtained: Ω₂=1.71×10⁻²⁰ cm², Ω₄=1.39×10⁻²⁰ cm², Ω₆=0.74×10⁻²⁰ cm² for π-polarization, and Ω₂=1.77×10⁻²⁰ cm², Ω₄=1.44×10⁻²⁰ cm², Ω₆=0.65×10⁻²⁰ cm² for σ-polarization. The emission cross-section σ_em was calculated to be 4.75×10⁻²¹ cm² for π-polarization at 1536 nm and 6.30×10⁻²¹ cm² for σ-polarization at 1537 nm. The investigated results showed that Er³⁺:Sr₃Y(BO₃)₃ crystal may be regarded as a potential laser host material for 1.55 μm IR solid-state lasers.     

Upconversion fluorescence property of Er/Yb-codoped novel bismuth-germanium glass

Infrared-to-visible upconversion fluorescence property of Er³⁺/Yb³⁺-codoped novel bismuth-germanium glass under 975 nm LD excitation has been studied. Intense green and red emissions centered at 525, 546 and 657 nm, corresponding to the transitions ²H_11/2→⁴I_15/2, ⁴S_3/2→⁴I_15/2, and ⁴F_9/2→⁴I_15/2, respectively, were observed at room temperature. The quadratic dependence of the 525, 546 and 657 nm emissions on excitation power indicates that a two-photon absorption process occurs. The structure of the bismuth-germanium glass has been investigated by peak-deconvolution of FT-Raman spectrum, and the structural information was obtained from the peak wavenumbers. This novel bismuth-germanium glass with low maximum phonon energy (∼750 cm⁻¹) can be used as potential host material for upconversion lasers.     

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.     

Influence of carbon templates and Yb concentration on red and green luminescence of uniform Y2O3:Yb/Er hollow microspheres

Uniform Yb³⁺ and Er³⁺-codoped Y₂O₃ hollow microspheres were synthesized via urea co-precipitation using carbon spheres as templates. Intense red emission (⁴F_9/2→⁴I_15/2) and weak green emission (²H_11/2, ⁴S_3/2→⁴I_15/2) of Er³⁺ were observed for the Yb³⁺ and Er³⁺-codoped Y₂O₃ hollow microspheres under 980 nm infrared excitation. The integrated intensity of visible emission and the ratio of red to green were found to be strongly dependent on the amount of carbon sphere templates and the concentration of Yb³⁺ ions. The amount of carbon sphere templates also plays an important role in adjusting the size of crystallite. Multi-phonon relaxation resulted from the absorbents (OH⁻ and CO₃²⁻) on the surface of the crystallite, and efficient occur of energy transfer processes and cross-relaxation between Er³⁺ and Yb³⁺ are responsible for the enhancement of intensity ratio of red to green emission. Interestingly, for higher concentration of Yb³⁺ ions, the green emission is assigned to a three-phonon process in Y₂O₃:Yb/Er hollow microspheres, which also could result in the increase of the red to green emission ratio. An explanation to account for these behaviors was presented.     

Investigation of energy transfer and frequency upconversion in Ho/Yb co-doped tellurite glasses

A serials of Ho³⁺/Yb³⁺ co-doped tellurite glasses by pumping 970 nm laser diode (LD) were demonstrated to obtain a high efficiency of infrared-to-visible upconversion. Two intense emission bands were observed in Ho³⁺/Yb³⁺ co-doped tellurite glasses centered at 549 and 664 nm corresponding to Ho³⁺: ⁵S₂(⁵F₄)→⁵I₈ and ⁵F₅→⁵I₈ transitions, respectively. The upconversion intensities of red and green emissions in Ho³⁺/Yb³⁺ co-doped glasses were enhanced largely when increasing Yb₂O₃ content. The dependence of upconversion intensities on excitation power and the possible upconversion mechanisms had been evaluated by a proper rate equation model. The energy transfer coefficients were estimated by fitting the simulated curves to the measured ones. The obtained three energy transfer coefficients C_D2, C_D3 and C_D4 were C_D2=5.0×10⁻¹⁸ cm³/s, C_D3=1.5×10⁻¹⁷ cm³/s, C_D4=9.0×10⁻¹⁷ cm³/s.     

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.     

Structural and upconversion fluorescence properties of Er/Yb-codoped oxychloride lead-germanium-bismuth glass

Structural and infrared-to-visible upconversion fluorescence properties of Er³⁺/Yb³⁺-codoped oxychloride lead-germanium-bismuth glass have been studied. The Raman spectrum investigation indicates that PbCl₂ plays an important role in the formation of glass network, and has an important influence on the upconversion luminescence owing to lower phonon energy. Intense green and red emissions centered at 525, 546, and 657 nm, corresponding to the transitions ²H_11/2→⁴I_15/2, ⁴S_3/2→⁴I_15/2, and ⁴F_9/2→⁴I_15/2, respectively, were observed at room temperature. The quadratic dependence of the 525, 546, and 657 nm emissions on excitation power indicates that a two-photon absorption process occurs under 975 nm excitation.     

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.     

The effect of Y co-doping on the persistent up-conversion luminescence of the ZrO2:Yb,Er nanomaterials

The effect of the defects due to the charge compensation obtained with the yttrium co-doping to the ZrO₂:Yb³⁺,Er³⁺ up-converting phosphors was studied. The materials were prepared with the combustion method. The materials purity was analyzed with the FT-IR spectroscopy. The crystal structure was studied with the X-ray powder diffraction and the crystallite sizes were estimated with the Scherrer formula. Up-conversion luminescence was excited at room temperature with an IR-laser at 970 nm. The up-conversion luminescence spectra showed red (650-685 nm) and green emission (520-560 nm) due to the ⁴F_9/2→⁴I_15/2 and (²H_11/2,⁴S_3/2)→⁴I_15/2 transitions of Er³⁺, respectively. Persistent up-conversion luminescence was observed both in the Yb³⁺,Er³⁺ and Y³⁺,Yb³⁺,Er³⁺ doped materials.     

Ultraviolet upconversion luminescence enhancement in Yb/Er-codoped Y2O3 nanocrystals induced by tridoping with Li ions

Ultraviolet (UV) upconversion (UC) luminescence in Yb³⁺/Er³⁺-codoped yttrium oxide (Y₂O₃) nanocrystals can be enhanced by orders of magnitude via tridoping further with Li⁺ ions under diode laser excitation of 970 nm. Sensitized three-photon UC radiations at 390 and 409 nm, corresponding to the ⁴G_11/2→⁴I_15/2 and ⁴H_9/2→⁴I_15/2 of Er³⁺ ions, respectively, present an enhancement time of about 33 times, which is larger than the 24 times enhancement for the UC green radiation. The UV UC radiation at 320 nm that corresponds to the ²P_3/2→⁴I_15/2 of Er³⁺ ions has also been greatly enhanced. Theoretical calculations interpret that all the observed enhancement times of UV UC radiations arise from the prolonged lifetimes of their intermediate states.     

Broadband amplification and upconversion luminescence properties of Er/Yb co-doped fluorophosphate glass

Broadband and upconversion properties were studied in Er³⁺/Yb³⁺ co-doped fluorophosphate glasses. Large Ω₆ and S_ed/(S_ed+S_md) values and the flat gain profile over 1530-1585 nm indicate the good broadband properties of the glass system. And a premise of using Ω₆ as a parameter to estimate the broadband properties of the glasses is proposed for the first time to our knowledge. Results showed that fluorescence intensity, upconversion luminescence intensity, the intensity ratio of red/green light (656 nm/545 nm) are closely related to the Yb³⁺:Er³⁺ ratio and Er³⁺ concentration, and the corresponding calculated lifetime of ⁴F_9/2 and ⁴S_3/2 states for red and green upconversion samples proves this conclusion. The upconversion mechanism is also discussed.     

Spectral properties of Nd:Ca2Nb2O7 crystal

This paper reports the spectral properties of Nd³⁺:Ca₂Nb₂O₇. The spectral parameters of Nd³⁺ in Nd³⁺:Ca₂Nb₂O₇ crystal have been investigated based on Judd-Ofelt theory. The spectral parameters were obtained. The parameters of line strengths Ω_λ are Ω₂=4.967×10⁻²⁰ cm², Ω₄=5.431×10⁻²⁰ cm², Ω₆=5.693×10⁻²⁰ cm². The radiative lifetime, the fluorescence lifetime and the quantum efficiency are 122 μs, 103 μs and 84.4%, respectively. The fluorescence branch ratios calculated: β₁=0.425, β₂=0.479, β₃=0.091, β₄=0.004. The emission cross section at 1068 nm is 6.204×10⁻²⁰ cm².     

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.     

Spectroscopic analysis of Er transition in Mg/Er-codoped LiNbO3 crystal

We present a Judd-Ofelt spectroscopic analysis on the Mg/Er-codoped congruent lithium niobate (LiNbO₃) crystals. The Judd-Ofelt model is applied to the room temperature unpolarized absorption intensities of Er³⁺ ions on eleven transition bands to determine their intensity parameters: Ω₂=2.36×10⁻²⁰ cm², Ω₄=0.76×10⁻²⁰ cm², Ω₆=0.30×10⁻²⁰ cm² in Er:LiNbO₃ crystal heavily codoped with MgO. The radiative lifetime of ²H_9/2 becomes longer when MgO is added into Er:LiNbO₃ crystal. The experimental lifetimes are obtained using microsecond time-resolved spectra at 400 nm femtosecond pulse excitation to predict radiative quantum efficiency. Combining higher radiative quantum efficiency with longer radiative lifetime, we conclude that Mg/Er-codoped LiNbO₃ crystals are more suitable than Er: LiNbO₃ ones in laser materials.     

Controlled Stark shifts in Er-doped crystalline and amorphous waveguides for quantum state storage

We present measurements of the linear Stark effect on the ⁴I_15/2 → ⁴I_13/2 transition in an Er³⁺-doped proton-exchanged LiNbO₃ crystalline waveguide and an Er³⁺-doped silicate fiber. The measurements were made using spectral hole burning techniques at temperatures below 4 K. We measured an effective Stark coefficient (Δμ_eχ)/(h) = 25 ± 1 kHz/V cm⁻¹ in the crystalline waveguide and  kHz/V cm⁻¹ in the silicate fiber. These results confirm the potential of erbium-doped waveguides for quantum state storage based on controlled reversible inhomogeneous broadening.