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.     

Infrared-to-visible up-conversion luminescence and energy transfer of RE3+/Yb3+(RE = Ho,Tm) co-doped SrIn2O4

Near-infrared excited up-conversion phosphors of RE³⁺/Yb³⁺(RE = Ho, Tm) co-doped SrIn₂O₄ were synthesized by a solid-state reaction method. X-ray diffraction analysis revealed the phase composition of those samples, and the up-conversion spectroscopic properties were studied in terms of up-conversion emission spectra. Under 980 nm near-infrared laser excitation, strong green emission with the peak at 546 nm was observed in SrIn₂O₄: Ho³⁺/Yb³⁺, which can be assigned to the characteristic ⁵S₂(⁵F₄) → ⁵I₈ transition of Ho³⁺. Furthermore, SrIn₂O₄: Tm³⁺/Yb³⁺ showed bright blue emission with the peak at 486 nm, which is associated with the ¹G₄ → ³H₆ transition of Tm³⁺. The UC power studies indicated that the luminescence of SrIn₂O₄: Ho³⁺/Yb³⁺ and SrIn₂O₄: Tm³⁺/Yb³⁺ are attributed to two-photon and three-photon process, respectively. The possible UC luminescence mechanism and energy transfer in SrIn₂O₄: RE³⁺/Yb³⁺ were discussed.     

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.     

Microwave sol–gel derived NaCaGd(MoO4)3:Er3+/Yb3+ phosphors and their upconversion photoluminescence properties

Ternary molybdate NaCaGd_1−x(MoO₄)₃:Er³⁺/Yb³⁺ phosphors with the proper doping concentrations of Er³⁺ and Yb³⁺ (x = Er³⁺ + Yb³⁺, Er³⁺ = 0, 0.05, 0.1, 0.2 and Yb³⁺ = 0, 0.2, 0.45) were successfully synthesized by microwave sol–gel method for the first time. Well-crystallized particles formed after heat-treatment at 900 °C for 16 h showed a fine and homogeneous morphology with particle sizes of 3–5 μm. The optical properties were examined comparatively using photoluminescence emission and Raman spectroscopy. Under excitation at 980 nm, the doped particles exhibited a strong 525-nm emission band, a weak 550-nm emission band in the green region, which correspond to the ²H_11/2 → ⁴I_15/2 and ⁴S_3/2 → ⁴I_15/2 transitions, and a very weak 655-nm emission band in the red region, which corresponds to the ⁴F_9/2 → ⁴I_15/2 transition. The optimal Yb³⁺:Er³⁺ ratio was obtained to be 9:1, as indicated by the composition-dependent quenching effect of Er³⁺ ions. The pump power dependence of upconversion emission intensity and Commission Internationale de L’Eclairage chromaticity coordinates of the phosphors were evaluated in detail.     

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.     

Upconversion photoluminescence properties of SrY2(MoO4)4:Er3+/Yb3+ phosphors synthesized by a cyclic microwave-modified sol–gel method

SrY_2−x(MoO₄)₄:Er³⁺/Yb³ phosphors with doping concentrations of Er³⁺ and Yb³⁺ (x = Er³⁺ + Yb³⁺, Er³⁺ = 0.05, 0.1, 0.2 and Yb³⁺ = 0.2, 0.45) have been successfully synthesized by a cyclic microwave-modified sol–gel method, and the upconversion photoluminescence properties have been investigated. Well-crystallized particles showed a fine and homogeneous morphology with particle sizes of 1–3 μm. Under excitation at 980 nm, SrY₂(MoO₄)₄:Er³⁺/Yb³⁺ particles exhibited a strong 525-nm, weak 550-nm emission bands in the green region, and a very weak 655-nm emission band in the red region. The possible mechanism of the green and red emissions was discussed in detail under consideration of a two-photon process. The Raman spectra of the particles indicated the presence of strong peaks at both higher and lower frequencies.     

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.     

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.     

Near infrared and charge transfer luminescence of trivalent ytterbium in KLa(PO3)4 powders

The polycrystalline powders of condensed polyphosphates KLa_(1 ? x)Yb_x(PO₃)₄ (x = 5, 10, 15, 20%) with linear chain were prepared by solid-state reaction. These samples were characterized by X-ray diffraction, FTIR and Raman scattering spectroscopies. The obtained powders are formed by single monoclinic phase of type III of condensed polyphosphate KLa(PO₃)₄ (KLP) crystallized with P2₁ space group. Lattice parameters varied as a function of the ytterbium concentration. As the Yb³⁺ concentration increased, the crystal lattice parameters were decreased. For the first time, near infrared (NIR) and UV–Visible spectroscopy of Yb³⁺ in KLa(PO₃)₄ powders, at room temperature, are carried out. In the IR range, a broad band relative to the fundamental ²F_5/2 → ²F_7/2 emission was registered. In the UV–Visible spectra, two bands typical of the Yb³⁺ charge transfer band (CTB) luminescence are observed. The registered decay times of these two emission types showed low sensibility to the Yb³⁺ concentration in KLa(PO₃)₄.     

Laser induced optical heating from Yb3+/Ho3+:Ca12Al14O33 and its applicability as a thermal probe

Yb³⁺/Ho³⁺ co-doped calcium aluminate phosphor has been synthesized using solution combustion process. Multicolored (blue, green and red) strong upconversion emission (λ_exc=980 nm) due to Ho³⁺ ion is observed which shows a color tunability (from green to red) with a variation in input laser power. The color tunability has been attributed to be due to the induced heating in the local volume of the sample and the temperature produced has been estimated using the fluorescence intensity ratio (FIR) method. The sample shows temperature sensing behavior and more importantly the temperature could be sensed through two pairs of thermally coupled levels, one lying in the green region (⁵F₄/⁵S₂→⁵I₈) and the other in the blue region (⁵G₄/⁵G₅→⁵I₈). The temperature sensing through the blue pair of levels is novel in itself. The material thus prepared serves as temperature sensor as well as a source for the production of heat in a localized volume.     

Ultraviolet to near-infrared downconversion in Yb3+–Na+ codoped Sr2CaWO6

This study investigated photoluminescent properties of Sr₂CaWO₆:Yb³⁺, Na⁺ phosphor. The samples were successfully synthesized via a solid-state reaction method with various doping concentrations. The phosphor can efficiently absorb ultraviolet photons of 250–350 nm and transfer its absorbed photon energy to Yb³⁺ ions. Then subsequent quantum cutting between WO₆ groups and Yb³⁺ ions takes place, down-converting an absorbed ultraviolet photon into two photons of 1007 nm radiations. Analyses of decay curves of different samples reveal an efficient energy transfer from WO₆ groups to Yb³⁺ ions. Cooperative energy transfer from host to Yb³⁺ ions is responsible for downconversion via lifetime analysis. Quantum efficiencies were calculated, and estimated maximum efficiency reached 190%. These phosphors combine wide wavelength absorption in the ultraviolet range with high quantum efficiency, enabling potential application of efficiency enhancement of Si solar cell.     

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.     

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.     

Synthesis and luminescence properties of Ho3+ doped Y2O3 submicron particles

This paper presents comprehensive results of the eco-friendly, large scale fabrication of nearly spherical Ho³⁺-doped Y₂O₃ submicron particles, synthesized using the urea homogeneous precipitation method. The dependence of the photoluminescence emission on the doping concentration was examined to determine the optimum Ho³⁺ concentration in the samples. X-ray diffraction data of the Y₂O₃:Ho³⁺ particles revealed a cubic Y₂O₃ structure. Field emission scanning electron microscopy confirmed the formation of nearly spherical shape particles with a mean diameter of 200±50 nm. The luminescence emission intensity significantly increased with increasing calcination temperature due to the improved crystallinity of the synthesized particles. Strong visible green-yellowish emission due to ⁵F₄; ⁵S₂–⁵I₈ Stokes transitions was observed under constant 450 nm excitation. Simple large scale fabrication along with the strong visible green-yellowish emission might give these particles wide area of applications.     

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.     

A promising novel orange–red emitting SrZnV2O7:Sm3+ nanophosphor for phosphor-converted white LEDs with near-ultraviolet excitation

A novel trivalent samarium doped SrZnV₂O₇ nanophosphors was developed via urea assisted solution combustion method using metal nitrates as initial raw materials. The qualitative and quantitative phase analysis was carried out using Rietveld refinement technique. It was found to crystallize in monoclinic lattice with the P12₁/n1 (14) space group. The photoluminescent spectral study of SrZnV₂O₇:Sm³⁺ revealed that the excitation of 405 nm yields the characteristic emission peaks at 569, 599, 640 and 702 nm due to ⁴G_5/2→⁶H_5/2, ⁴G_5/2→⁶H_7/2, ⁴G_5/2→⁶H_9/2 and ⁴G_5/2→⁶H_11/2 respectively. The optimum concentration of Sm³⁺ ion in SrZnV₂O₇ for best luminescence was found to be 2 mol%. The luminescence intensity was further enhanced by incorporating compensator charge R⁺ (R=Li, Na, and K) into the SrZnV₂O₇:0.02Sm³⁺ nanophosphor. The critical distance for non-radiative energy transfer was calculated to be 26.64 Å. Dipole–dipole (d–d) interactions were ascribed as the major factor responsible for concentration quenching arising from the over-doping of the activator ions. The results indicate that these nanophosphors are suitable candidate for PC-WLEDs using near UV excitation.     

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.     

Temporal dynamics of upconversion luminescence in Er3+, Yb3+ co-doped crystalline KY(WO4)2 thin films

Crystalline Er³⁺ and Yb³⁺ singly and doubly doped KY(WO₄)₂ thin films were grown by low-temperature liquid-phase epitaxy. Absorption, luminescence, excitation and temporal evolution measurements were carried out for both Er³⁺ and Yb³⁺ transitions from 10 K to room temperature. Green Er³⁺ upconversion luminescence was observed after Yb³⁺ and Er³⁺ excitation. The mechanisms responsible for the upconversion phenomena detected in each case were identified.     

Photoluminescence investigations of Li2SiO3:Ln (Ln=Er3+, Eu3+, Dy3+, Sm3+) phosphors

In this study, we report a comprehensive structural and photoluminescence (PL) study on lithium metasilicate (Li₂SiO₃) phosphor ceramics doped with four rare earth (RE) ions. X-ray diffraction (XRD) patterns show a dominant phase, characteristic of the orthorhombic structure Li₂SiO₃ compound and the presence of dopants has no effect on the basic crystal structure of the material. The first excited state Er³⁺ luminescence at 1.54 μm arises from a sharp atomic-like radiative transition between the ⁴I_13/2 state and the ⁴I_15/2 state (ground level) under a 532 nm line of an Ar ion laser excitation. Sm doped samples showed Sm³⁺ emission characteristics corresponding to the some ⁴G_5/2→⁶H_j (j=5/2,9/2,11/2) transitions indicating a strong crystal-field effect. PL spectra of Eu doped material exhibited peaks corresponding to the ⁵D₀→⁷F_j (j=0,1,2,3 and 4) transitions under 405 nm excitation. The dominant red color emission at 612 nm from the hypersensitive (⁵D₀→⁷F₂) transition of Eu³⁺ indicates the inversion antisymmetry crystal field around Eu³⁺ ion, which is favorable to improve the red color purity. Dy doped samples showed the Dy³⁺ emission characteristic due to the ⁴F_9/2→⁶H_13/2 transition. Their relative intensity ratios also suggested the presence of a symmetric environment around the metal ion. We suggest that lithium metasilicate has enough potential candidates to be a phosphor material.     

Enhanced 2.0 μm emission in Ho3+/Yb3+ co-doped silica-germanate glass

A detailed investigation on thermal and spectroscopic properties of different Ho³⁺/Yb³⁺ concentration ratios in silica-germanate glasses is displayed. According to the measurement of thermal properties, the host glass possesses high transition temperature (585 °C) as well as the large ΔT(155 °C). The 2.0 μm fluorescence can be obtained from all the samples. Maximum stimulated emission cross-section of around 2.0 μm is 0.56 × 10⁻²⁰ cm² of Ho³⁺ as calculated by McCumber theory. Besides, the underlying mechanism is analyzed by means of fluorescence spectra. Thus, desirable thermal properties and spectroscopic characteristics of Ho³⁺/Yb³⁺ co-doped silica-germanate glass is a promising material in 2.0 μm emission.