Hydrothermal synthesis and the enhanced blue upconversion luminescence of NaYF4:Nd3+,Tm3+,Yb3+

Nd³⁺, Tm³⁺ and Yb³⁺ co-doped NaYF₄ upconversion (UC) material was synthesized by the hydrothermal method. The structure of the sample was characterized by the X-ray diffraction, and its UC luminescence properties were investigated in detail. Under the 980 nm semiconductor laser excitation, its UC spectra exhibited distinct emission peaks at 451 nm, 475 nm and 646 nm respectively. On the basis of the comparison of UC spectra between NaYF₄:Nd³⁺,Tm³⁺,Yb³⁺ and NaYF₄:Tm³⁺,Yb³⁺, it was indicated that the existence of Nd³⁺ ion enhanced the blue emission intensity. The law of luminescence intensity versus pump power proved that the blue emission at 475 nm, and the red emission at 646 nm were the two-photon processes, while the blue emission at 451 nm was a three-photon process.     

Synthesis and up-conversion luminescence properties of Ho3+, Yb3+ co-doped BaLa2ZnO5

Up-conversion phosphors BaLa₂ZnO₅ co-doped with Ho³⁺/Yb³⁺ were synthesized by high temperature solid-state reaction method. The phase composition of the phosphors was characterized by X-ray diffraction (XRD). The structure of BaLa₂ZnO₅: 0.75% Ho/15% Yb phosphor was refined by the Rietveld method and results showed the decreased unit cell parameters and cell volume after doping Ho³⁺ and Yb³⁺, indicating Ho³⁺ and Yb³⁺ have successfully replaced La³⁺. Under the excitation of 980 nm diode laser, the strong green and weak red up-conversion emissions centered at 548 nm, 664 nm and 758 nm were observed, which originating from ⁵S₂, ⁵F₂→⁵I₈, ⁵F₄→⁵I₈ and ⁵S₂, ⁵F₂→⁵I₇ transitions of Ho³⁺ ions, respectively. The optimum doping concentrations of Ho³⁺ and Yb³⁺ were determined to be 0.75% and 15%, and the corresponding Commission International de L'Eclairage (CIE) coordinates are calculated to be x=0.298 and y=0.692. The related UC mechanism of Ho³⁺/Yb³⁺ co-doped BaLa₂ZnO₅ depending on pump power was studied in detail. The results indicate that BaLa₂ZnO₅: Ho³⁺/Yb³⁺ can be an effective candidate for up-conversion yellowish-green light emitter.     

Upconversion luminescence in Tm3+/Yb3+co-doped lead tungstate tellurite glasses

This work reports the upconversion luminescence properties of Tm³⁺/Yb³⁺ ions in lead tungstate tellurite (LTT) glasses. Judd–Oflet intensity parameters have been obtained from the absorption band intensities of Tm³⁺ singly-doped and Tm³⁺/Yb³⁺ co-doped LTT glasses. The spontaneous emission probabilities, radiative lifetimes and branching ratios for ¹G₄ and ³H₄ emission levels of Tm³⁺ have been determined. Upconversion luminescence has been observed by exciting the samples at 980 nm (Yb³⁺:²F_7/2→²F_5/2) at room temperature. Four upconversion emission bands corresponding to the ¹G₄→³H₆ (477 nm), ¹G₄→³F₄ (651 nm), ¹G₄→³H₅ (702 nm) and ³H₄→³H₆ (810 nm) transitions have been identified. The relative variation in the intensities of upconversion bands, the different channels responsible for upconversion spectra and the effect of Yb³⁺ ions concentration on the upconversion luminescence of Tm³⁺ ions have also been discussed.     

Microwave sol-gel process of KGd(WO4)2:Ho3+/Yb3 phosphors and their upconversion photoluminescence properties

Double tungstate KGd_1−x(WO₄)₂:Ho³⁺/Yb³⁺ phosphors with doping concentrations of Ho³⁺ and Yb³⁺ (x=Ho³⁺+Yb³⁺, Ho³⁺=0.05, 0.1, 0.2 and Yb³⁺=0.2, 0.45) were successfully synthesized by the microwave sol–gel method, and the upconversion mechanisms were investigated in detail. The synthesized particles formed after heat-treatment at 900 °C for 16 h showed a well crystallized morphology with particle sizes of 2–5 μm. Under excitation at 980 nm, the UC intensities of KGd_0.7(WO₄)₂:Ho_0.1Yb_0.2 and KGd_0.5(WO₄)₂Ho_0.05Yb_0.45 particles exhibited yellow emissions based on a strong 550-nm emission band in the green region and a strong 655-nm emission band in the red region, which were assigned to the ⁵S₂/⁵F₄→⁵I₈ and ⁵F₅→⁵I₈ transitions, respectively. The Raman spectra of the doped particles indicated the presence of strong peaks at higher frequencies of 764, 812, 904, 984, 1050, 1106, 1250 and 1340 cm⁻¹ induced by the disorder of the [WO₄]²⁻ groups with the incorporation of the Ho³⁺ and Yb³⁺ elements into the crystal lattice or by a new phase formation.     

Spectroscopic properties of Tm3+/Ho3+ co-doped NaLa(WO4)2 single crystal

Tm³⁺/Ho³⁺ co-doped NaLa(WO₄)₂ single crystal was successfully grown by the Czochralski method. The crystal was characterized by room temperature absorption spectra, fluorescence spectra around 2 μm, up-conversion fluorescence and luminescence decay measurements. Spectroscopic properties related to the laser operation around 2 μm of Ho³⁺ ions have been evaluated. The energy level scheme and energy transfer processes of Tm³⁺ and Ho³⁺ were analyzed. The obtained spectroscopic results show the crystal is a potentially host for Ho³⁺ 2 μm infrared laser.     

Towards efficient upconversion and downconversion of NaYF4:Ho3+,Yb3+ phosphors

NaYF₄ microcrystals co-doped with Ho³⁺ and Yb³⁺ were prepared by a facile hydrothermal synthesis. The products were characterized by X-ray diffractometer, scanning electron microscopy, and photoluminescence spectroscopy. Upon excitation with a 980 nm laser diode, the sample shows an intense green upconversion emission centered at 540 nm corresponding to the ⁵S₂→⁵I₈ transition of Ho³⁺. The quadratic dependence of the green emission intensity on the excitation power reveals a two-phonon upconversion process. On the contrary, upon excitation with 448 nm, both visible and near-infrared emissions peaked at 483, 540, 644, 749, and 978 nm are simultaneously observed, which could be assigned to the electronic transitions of Ho³⁺: ⁵F₃→⁵I₈, ⁵S₂→⁵I₈, ⁵F₅→⁵I₈, ⁵S₂→⁵I₇, and Yb³⁺: ²F_5/2→²F_7/2, respectively. The energy transfer processes between Ho³⁺ and Yb³⁺ ions and the involved mechanisms have been investigated and discussed.     

Blue upconversion luminescence in 12 CaO·7 Al2O3:Tm3 +/Yb3 + polycrystals

The effect of Yb^3 + concentration on the fluorescence of 12 CaO·7 Al₂O₃:Tm^3 +/Yb^3 + polycrystals is investigated. Under the excitation of 980 nm laser, the strong blue (477 nm) emission band is observed and attributed to ¹G₄ → ³H₆ of Tm^3 +. The ratio of blue to red emission increases with the increasing of Yb^3 + and remains constant at 10 mol% Yb^3 +. The pump dependence and upconversion mechanisms show that the two-photon cooperative upconversion process is responsible for the enhancement of the blue upconversion emission. The Commission Internationale de l'eclairage chromaticity coordinates (x, y) illustrate that the 12 CaO·7 Al₂O₃:1 mol% Tm^3 +/10 mol% Yb^3 + can emit high-purity blue light.     

Optical temperature sensor through infrared excited blue upconversion emission in Tm3 +/Yb3 + codoped Y2O3

An analysis of the intense blue upconversion emission at 476 and 488 nm in Tm^3 +/Yb^3 + codoped Y₂O₃ under excitation power density of 86.7 W/cm² available from a diode laser emitting at 976 nm, has been undertaken. Fluorescence intensity ratio (FIR) variation of temperature-sensitive blue upconversion emission at 476 and 488 nm in this material was recorded in the temperature range from 303 to 753 K. The maximum sensitivity derived from the FIR technique of the blue upconversion emission is approximately 0.0035 K^? 1. The results imply that Tm^3 +/Yb^3 + codoped Y₂O₃ is a potential candidate for the optical temperature sensor.     

Increase of the blue upconversion emission in YAG:Tm3+ nanopowders by codoping with Yb3+ ions

The YAG nanopowders were prepared by a co-precipitation method using nitrate and ammonium hydrogen carbonate as raw materials. To obtain homogenous precipitate, reverse-strike (adding salt solutions to the precipitant solution) technique was adopted. Therefore, single (Tm³⁺) and codoped (Tm³⁺–Yb³⁺) YAG nanopowders with a size between 40–90 nm have been obtained.Blue upconversion emission at around 480 nm has been found in YAG: Tm³⁺ nanopowders under excitation to the ³H₄ level of Tm³⁺ at around 800 nm. However, this upconversion emission in nanopowders codoped with Tm³⁺–Yb³⁺ ions is increased by a factor of about 10. The analysis of the temporal evolution of the involved levels and the dependence of the upconversion intensity on the pump power at 800 nm allowed to distinguish the upconversion mechanism. In YAG: Tm³⁺ nanopowders the upconversion mechanism is due to excited state absorption processes. However, in the codoped samples, Yb³⁺ ions acts as the sensitizers; in consequence, the blue upconversion is strongly increased.     

Synthesis and near-infrared luminescence properties of LaOCl:Nd3+/Yb3+

Near-infrared emitting phosphors LaOCl:Nd³⁺/Yb³⁺ were prepared by the solid-state method, and their structures and luminescent properties were investigated by using X-ray diffraction and photoluminescence analysis, respectively. The studies shows that tetragonal LaOCl:Nd³⁺/Yb³⁺ can be synthesized by the solid-state reaction at 600 °C for 3 h. Upon 353 nm UV excitation, LaOCl:Nd³⁺/Yb³⁺ sample shows strong near-infrared emission lines in the region of 1060–1150 nm (corresponding to ⁴F_3/2 → ⁴I_J′ transition of Nd³⁺, J′ = 9/2, 11/2, 13/2, 15/2) and 980–1050 nm (corresponding to ²F_5/2 → ²F_7/2 transition of Yb³⁺). The decreasing emission intensity of Nd³⁺ with increasing doping concentration of Yb³⁺ proved the energy transfer in LaOCl:Nd³⁺/Yb³⁺. The possible near-infrared emission and energy transfer mechanism between Nd³⁺ and Yb³⁺, as well as the energy transfer efficiency of LaOCl:Nd³⁺/Yb³⁺ were discussed.     

Near-infrared broadband luminescence and energy transfer in Bi–Tm–Er co-doped lanthanum aluminosilicate glasses

The Bi–Tm–Er co-doped SiO₂–Al₂O₃–La₂O₃ (SAL) glasses, which exhibited a broadband near-infrared (NIR) emission, were investigated by the optical absorption and photoluminescence spectra. A super broadband NIR emission extending from 0.95 to 1.6 μm with a full-width at half-maximum (FWHM) of 430 nm which covered the whole O, E, S, C and L bands, was observed in Bi–Tm–Er co-doped samples under 808 nm excitation, as a result of the overlap of the Bi-related emission band (centered at 1270 nm) and the emission from Tm^{3+ 3}H₄→³F₄ transition (1450 nm) as well as Er^{3+ 4}I_13/2→⁴I_15/2 transition (1545 nm). In addition, a super broadband emission with amplitude relatively flat from 0.95 to 2.1 μm has been observed. The possible energy transfer between Bi-related centers, Tm³⁺ ions and Er³⁺ ions was proposed.     

Spectroscopic characteristics of Tm3+ in Tm and Tm,Nd, Yb:Sc2O3 ceramic

The spectroscopic investigation of Tm³⁺ or (Nd, Yb, Tm)-doped Sc₂O₃ transparent ceramics, as laser-active media for visible and IR emission, was performed. The spectra are dominated by Tm³⁺ ions in sites of C₂ symmetry and an energy level scheme and other spectral parameters were determined. The strong concentration quenching of ³H₄ level emission in Tm:Sc₂O₃ at 300 K is discussed by considering the resonant cross-relaxation (³H₄→³F₄)?(³H₆→³F₄) process and multipolar interactions of various orders. The main energy-transfer processes leading to the blue upconversion emission from the ¹G₄ Tm³⁺ level in (Tm, Nd, Yb):Sc₂O₃ ceramic, under pulsed pumping at 808.3 nm were evidenced.     

Synthesis and luminescence properties of Gd6MoO12:Yb3+, Er3+ phosphor with enhanced photoluminescence by Li+ doping

Yb³⁺/Er³⁺ co-doped Gd₆MoO₁₂ and Yb³⁺/Er³⁺/Li⁺ tri-doped Gd₆MoO₁₂ phosphors were prepared by adjusting the annealing temperature via the high temperature solid-state method. Under the excitation of 980 nm semiconductor, the upconversion luminescence properties were investigated and discussed. In the experimental process, we get the optimum Yb³⁺ concentration and the concentration quench effect will happen while the concentration extends the given region. According to the Yb³⁺ concentration quenching effects, the critical distance between Yb³⁺ ions had been calculated. The measured UC luminescence exhibited a strong red emission near 660 nm and green emission at 530 nm and 550 nm, which are due to the transitions of Er³⁺(⁴F_9/2, ²H_11/2, ⁴S_3/2) → Er³⁺(⁴I_15/2). Then the effect of excitation power density in different regions on the upconversion mechanisms was investigated and the calculated results demonstrate that the green and red upconversion is a two-photon process. A possible mechanism was discussed. After Li⁺ ions mixing, the upconversion emission enhanced largely, and the optimum Li⁺ concentration was obtained while fixed the Yb³⁺ and Er³⁺ on the above optimum concentration. This enhancement owns to the decrease of the local symmetry around Er³⁺ after Li⁺ ions doping into the system. This result indicates that Li⁺ is a promising candidate for improving luminescence in some case.     

Up conversion luminescence of Yb3+–Er3+ codoped CeO2 nanocrystals with imaging applications

The effects of Yb³⁺ doping on up conversion in Yb³⁺–Er³⁺ co-doped cerium oxide nanocrystals are reported. Green emission around 545 and 560 nm attributed to the ²H_11/2, ⁴S_3/2→⁴I_15/2 transitions and red emission around 660 and 680 nm due to ⁴F_9/2→ ⁴I_15/2 transitions under 975 nm excitation were studied at room temperature. Both green and red emission intensities increase as the Yb³⁺ concentration increases from 0%. Emission strength starts to decrease after the Yb³⁺ concentration exceeds a critical amount. The green emission strength peaks around 1% Yb³⁺ concentration while the red emission strength peaks around 4%. An explanation of competition between different decay mechanisms is presented to account for the luminescence dependence on Yb³⁺ concentration. Also, the application of up converting nanoparticles in biomedical imaging is demonstrated.     

Comparative study of the spectroscopic properties of Yb3+/Er3+ codoped tellurite glasses modified with R2O (R=Li,Na and K)

Spectroscopic characterization of Yb³⁺/Er³⁺ codoped TeO₂–R₂O–ZnO–Ln₂O₃ glasses as a function of network modifiers (R=Li, Na and K) has been investigated. The Judd–Ofelt parameters (Ω_t), quantum efficiency in near infrared (1.55 μm) and visible up-conversion (546 and 660 nm) and quality factor spectroscopy (χ) were calculated. Three up-conversion emission bands centered at 525, 546 and 660 nm were observed as maxima for glasses containing potassium. The measured lifetime of ⁴I_13/2, ⁴F_9/2 and ⁴S_3/2 from Er³⁺ and ⁴F_5/2 from Yb³⁺ levels increased when potassium (K) replaced lithium (Li) and Na. The maximum emission cross-section (ECS) for ⁴I_13/2→⁴I_15/2 transition of Er³⁺ was calculated to be 1.02×10^?20 cm² for TeO₂–Li₂O–ZnO–Ln₂O₃ glasses. The energy transfer efficiency (ET) from Yb³⁺ to Er³⁺, (⁴F_5/2)+(⁴I_15/2)→(⁴F_7/2)+(⁴I_13/2), was calculated using the measured lifetimes of Yb³⁺ with and without the presence of acceptor (Er³⁺). The maximum calculated ET was 58% for 0.25 mol% of Er³⁺ and 3 mol% of Yb³⁺ for TeO₂–K₂O–ZnO–Ln₂O₃ glass composition.     

Intense 974 nm emission from ErxYb2−xSi2O7 films through efficient energy transfer up-conversion from Er3+ to Yb3+ for Si solar cell

The optical properties of the Er_xYb_2?xSi₂O₇ thin films were investigated by photoluminescence measurements and the intense 974 nm light emission was observed. The 974 nm emission was mainly from the transition ²F_5/2 to ²F_7/2 level of Yb³⁺ upon exploring energy-transfer via up-conversion at Er^{3+ 4}I_13/2 level. Under 972 nm excitation, the lifetime at Er^{3+ 4}I_13/2 level reaches up to 4 ms for film containing 2 at% Er³⁺, while decreases to about 20 μs as the film is pumped by 488 nm. This confirmed that the energy transfer up-conversion process was the dominant transition at Er^{3+ 4}I_13/2 level. This may be of interest to improve the solar cells′ efficiency by placing this film at the rear of cell, converting the near-infrared photons between 1480 nm and 1580 nm to just above the Si bandgap.     

White up-conversion emission in Ho/Tm/Yb tri-doped glass ceramics embedding BaF2 nanocrystals

Ho³⁺/Tm³⁺/Yb³⁺ tri-doped glass ceramics with white light emitting have been developed and demonstrated. Pumped by 980 nm laser diode (LD), intensive red, green and blue up-conversions (UC) were obtained. The green emission is assigned to Ho³⁺ ion and the blue emission is assigned to Tm³⁺ ion, whereas the red emission is the combination contribution of the Ho³⁺ and Tm³⁺ ions. The RGB intensities could be adjusted by tuning the rare-earth ion concentration and pump power intensity. Thus, multicolor of the luminescence, including perfect white light with CIE-X=0.329 and CIE-Y=0.342 in the 1931 CIE chromaticity diagram can be obtained in 0.15 Ho³⁺/0.2Tm³⁺/3Yb³⁺ tri-doped glass ceramics embedding BaF₂ nanocrystals pumped by a single infrared laser diode source of 980 nm at 500 mW. The up-conversion luminescence mechanism of Yb³⁺ sensitize Ho³⁺ and Tm³⁺ ions and the energy transfer from Ho³⁺ to Tm³⁺ in oxy-fluoride silicate glass ceramics were analyzed.     

Quasi-one dimensional Er3+–Yb3+ codoped single-crystal MoO3 ribbons: Synthesis,characterization and up-conversion luminescence

The quasi-one dimensional (Q1D) Er³⁺–Yb³⁺ codoped single-crystal MoO₃ ribbons with width range from 1 to 5 μm, and maximum length about 30 μm have been synthesized by the vapor transport method. The samples were characterized using X-ray diffraction, scanning electron microscopy, transmission electron microscope, and luminescence spectra. By a 975 nm laser diode (LD) as excitation source, the blue, green and red emission bands centered at about 408, 532, 553 and 657 nm were detected, which attributed to the ²H_9/2 → ⁴I_15/2, ²H_11/2, ⁴S_3/2 → ⁴I_15/2 and ⁴F_9/2 → ⁴I_15/2 transitions of Er³⁺, respectively. The three-, and two-photon process was responsible for the blue, green and red up-conversion emissions mechanism for the Q1D Er³⁺–Yb³⁺ codoped single-crystal MoO₃ ribbons, respectively. The results suggested that the Q1D Er³⁺–Yb³⁺ codoped single-crystal MoO₃ ribbons will have potential applications in remote bio-imaging and surface enhanced Raman scattering.     

Positive influence of Tm3+ on effective Er3+: 3 μm emission in fluoride glass under 980 nm excitation

Er³⁺ and Tm³⁺ singly doped and codoped new fluoride glasses were prepared by traditional melt-quenching method. Efficient 3 μm emission was obtained under 980 nm laser excitation. It is worthy to notice that one of the two ions can be the sensitizer to the other one by depressing the Er³⁺: 1.5 μm emission through the energy transfer process from Er³⁺:⁴I_13/2 level to Tm³⁺:³F₄ level. On the basis of measured absorption spectra, the Judd-Ofelt intensity parameters and radiation emission probability were calculated to evaluate the spectroscopic properties. Additionally, the micro-parameters together with the phonon assistance of Er³⁺:⁴I_13/2 → Tm³⁺:³F₄ and Er³⁺:⁴I_11/2 → Tm³⁺:³H₅ processes were quantitatively analyzed by using Dexter model. The theoretical micro-parameters results meet well with the experiments which indicates that Er³⁺/Tm³⁺ codoped fluoride glass is a potential kind laser glass for 3 μm laser.     

Infrared broadband emission of bismuth–thulium co-doped lanthanum–aluminum–silica glasses

The Bi–Tm co-doped SiO₂–Al₂O₃–La₂O₃ (SAL) glasses, which exhibited a broadband near-infrared (NIR) emission was investigated by the optical absorption and photoluminescence spectra. The super broadband near-infrared emission from 1000 to 2100 nm, which covered the whole O, E, S, C and L bands, was observed in the Bi–Tm co-doped samples, as a result of the overlap of the Bi-related emission band (centered at 1270 nm) and the emission from Tm^{3+ 3}H₄→³F₄ transition (1440 nm) as well as Tm^{3+ 3}F₄→³H₆ transition (1800 nm). Relative luminescence intensity at 1270, 1440 and 1800 nm wavelength varied depending on the mixing ratio of Bi and Tm and the full-width at half-maximum (FWHM) extending from 1000 to 1600 nm could be 400 nm. These results indicated that Bi–Tm co-doped SiO₂–Al₂O₃–La₂O₃ glasses could provide potential applications in tunable lasers as well as the broadband optical amplifiers in WDM system.