Emission and Absorption Cross Sections at 810 and 860 nm Bands of Er3+ in LiNbO3 Crystal

We have measured the unpolarized and polarized emission spectra of ⁴I_9/2→⁴I_15/2 (810 nm) and ⁴S_3/2→⁴I_13/2 (860 nm) electronic transitions of Er³⁺ in LiNbO₃ crystal under different incident directions and polarization states of excitation beam. From the measured emission spectra, the emission and absorption cross‐section spectra were calculated based upon McCumber theory. It is found that Er³⁺ electronic transition shows interesting excitation beam direction effect in polarization dependence, spectral shape, and cross‐section value. Both transitions are highly π‐polarized as the excitation beam was aligned perpendicular to the optical axis of crystal while being highly σ‐polarized as the excitation beam was oriented parallel to the optical axis of crystal. The spectral shape in the case of the perpendicular excitation is very different from that in the case of parallel excitation. The cross‐section value in the perpendicular excitation case is at least 1.5 times larger than that in the parallel excitation case. These excitation direction effects are independent of the polarization state of excitation light, and are attributed to the selective Er³⁺ site excitation. In addition, the Er³⁺ 860 nm emission lifetime was measured to be 27 ± 5 μs and the quantum efficiency of the emission is 2.5%.     

Spectroscopic and energy transfer mechanism of Er3+, Pr3+-codoped ZBYA glass

Absorption spectra, emission spectra and the rate parameters of the energy-exchange processes relevant to the ⁴I_11/2→⁴I_13/2 laser transition in Er³⁺/Pr³⁺- codoped ZBYA(ZrF₄–BaF₂–AlF₃–YF₃) glass were presented. Intensive 2.7 μm emission was obtained in the codoped glass and the optimized concentration ratio of Pr³⁺ to Er³⁺ was found to be 0.1:1. With the presence of Pr³⁺ ions, the intensities of the green and near-infrared emission were dramatically reduced to 1/15 and 1/21, respectively. The Er³⁺/Pr³⁺-codoped sample was found to have higher predicted spontaneous transition probability (16.57%) along with larger calculated emission cross section (14.6×10⁻²¹ cm²). These results suggest that the 2.7 μm emission of Er³⁺ ions could be achieved in ZBYA glass and codoping with Pr³⁺ could greatly improve the mid-infrared emission performance.     

Deep red upconversion photoluminescence in Er3+-doped Yb3Ga5O12 nanocrystalline garnet

The nanocrystalline single-phase Er³⁺-doped Yb₃Ga₅O₁₂ garnets have been prepared by the sol-gel combustion technique with a crystallite size of ≈30 nm. The presence of Yb³⁺ in garnet hosts allows their efficient excitation at the ≈977 nm wavelength. The Er³⁺ doping of Yb₃Ga₅O₁₂ garnet host results in deep red Er³⁺: ⁴F_9/2 → ⁴I_15/2 upconversion photoluminescence (UCPL) emission. The dominance of the red UCPL emission over the green Er³⁺: ⁴F_7/2/²H_11/2/⁴S_3/2 → ⁴I_15/2 component was investigated using the measurement of the steady-state and time-dependent Er³⁺ and Yb³⁺ emission spectra in combination with the power-dependent UCPL emission intensity. The proposed upconversion mechanism is discussed in terms of the Er³⁺ → Yb³⁺ energy back transfer process as well as Yb³⁺(Er³⁺) → Er³⁺ energy transfer and Er³⁺ ↔ Er³⁺ cross-relaxation processes. The studied Er³⁺-doped Yb₃Ga₅O₁₂ garnet may be utilized as a red upconversion emitting phosphor.     

Fabrication and Upconversion Luminescent Properties of Er3+‐Doped and Er3+/Yb3+ Codoped La2O2CN2 Nanofibers

La₂O₂CN₂:Er³⁺and La₂O₂CN₂:Er³⁺/Yb³⁺ upconversion (UC) luminescence nanofibers were successfully fabricated via cyanamidation of the respective relevant La₂O₃:Er³⁺ and La₂O₃:Er³⁺/Yb³⁺ nanofibers which were obtained by calcining the electrospun composite nanofibers. The morphologies, structures, and properties of the nanofibers are investigated. The mean diameters of La₂O₂CN₂:Er³⁺ and La₂O₂CN₂:Er³⁺/Yb³⁺ nanofibers are 179.46 ± 12.58 nm and 198.85 ± 17.07 nm, respectively. It is found that intense green and weak red emissions around 524, 542, and 658 nm corresponding to the ²H_11/2→⁴I_15/2, ⁴S_3/2→⁴I_15/2, and ⁴F_9/2→⁴I_l5/2 energy levels transitions of Er³⁺ ions are observed for La₂O₂CN₂:Er³⁺ and La₂O₂CN₂:Er³⁺/Yb³⁺ nanofibers under the excitation of a 980‐nm diode laser. Moreover, the emitting colors of La₂O₂CN₂:Er³⁺ and La₂O₂CN₂:Er³⁺/Yb³⁺ nanofibers are all located in the green region. The upconversion luminescent mechanism and formation mechanism of the nanofibers are also proposed.     

Splitting upconversion emission and phonon‐assisted population inversion of Ba2Y(BO3)2Cl:Yb3+, Er3+ phosphor

Upconversion (UC) peak of ⁴S_3/2→⁴I_15/2 transition of Er³⁺ is close to that of ²H_11/2→⁴I_15/2 transition. The UC emission splitting of Er³⁺ caused by coordination fields of host results in that it is difficult to confirm which transitions (⁴S_3/2→⁴I_15/2 or ²H_11/2→⁴I_15/2) are responsible for the splitting UC emission peaks. In this work, the UC luminescence peaks located at 524, 540, 551, 565, 662, 677, and 683 nm were observed in the Ba₂Y(BO₃)₂Cl:Yb³⁺, Er³⁺ phosphor upon the 980 nm excitation. The 524 and 540 nm UC emissions intensity were increased, while the 551 and 565 nm UC emissions intensity were decreased with the temperature increasing from 323 to 573 K, which is attributed to the phonon‐assisted population inversion from the ⁴S_3/2 to ²H_11/2 level. The temperature dependence of UC emission spectra demonstrated that the 524 and 540 nm UC emissions are from ²H_11/2→⁴I_15/2 transition, and 551 and 565 nm UC emissions are from the ⁴S_3/2→⁴I_15/2 transition. Temperature sensing property was characterized by the UC intensity ratio of the ²H_11/2→⁴I_15/2 transition to ⁴S_3/2→⁴I_15/2 transition. The Ba₂Y(BO₃)₂Cl:Yb³⁺,Er³⁺ phosphor has potential application as the non‐contact temperature sensor.     

Microwave Sol–Gel Synthesis of CaGd2(MoO4)4:Er3+/Yb3+ Phosphors and Their Upconversion Photoluminescence Properties

CaGd₂(MoO₄)₄:Er³⁺/Yb³⁺ phosphors with the 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 the microwave sol–gel method, and the crystal structure refinement and upconversion photoluminescence properties have been investigated. The synthesized particles, being formed after heat‐treatment at 900°C for 16 h, showed a well‐crystallized morphology. Under the excitation at 980 nm, CaGd₂(MoO₄)₄:Er³⁺/Yb³⁺ particles exhibited strong 525 and 550‐nm emission bands in the green region and a weak 655‐nm emission band in the red region. The Raman spectrum of undoped CaGd₂(MoO₄)₄ revealed about 15 narrow lines. The strongest band observed at 903 cm^?1 was assigned to the ν₁ symmetric stretching vibration of MoO₄ tetrahedrons. The spectra of the samples doped with Er and Yb obtained under 514.5 nm excitation were dominated by Er³⁺ luminescence preventing the recording Raman spectra of these samples. Concentration quenching of the erbium luminescence at ²H_11/2→⁴I_15/2 and ⁴S_3/2→⁴I_15/2 transitions in the CaGd₂(MoO₄)₄:Er³⁺/Yb³⁺ crystal structure was established to be approximately at the 10 at.% doping level.     

Down-conversion from Er3+-Yb3+ codoped CaMoO4 phosphor: A spectral conversion to improve solar cell efficiency

The present paper focuses on near infrared (NIR) down-conversion photoluminescence (PL) properties by studying the energy transfer mechanism between Er³⁺ and Yb³⁺ in CaMoO₄:Er³⁺, Yb³⁺ phosphors. We have successfully synthesized a series of Er³⁺ doped and Yb³⁺ codoped CaMoO₄ phosphors by hydrothermal method. The down-conversion of Er³⁺-Yb³⁺ combination with CaMoO₄ phosphor is designed to overcome the energy losses due to spectral mismatch when a high energy photon is incident on the Si-solar cell. The XRD, FESEM, EDX, PL, UV–Vis, Lifetime measurements were carried out to characterize the prepared down-converting phosphors. The crystallinity and surface morphology were studied by X-ray diffraction (XRD) and Field Emission Scanning Electron Microscopy (FESEM) techniques. The down-conversion PL spectra have been studied using 380 nm excitation wavelength. The Er³⁺ doped phosphors exhibit hypersensitive emission at 555 nm in the visible region due to ⁴S_3/2→⁴I_15/2 transition. The addition of Yb³⁺ into Er³⁺ doped CaMoO₄ attribute an emission at 980 nm due to ²F_5/2→²F_7/2 transition. The decrease in emission intensity in visible region and increase in NIR region reveals the energy transfer from Er³⁺ to Yb³⁺ through cross relaxation. The UV–Vis–NIR spectra shows the strong absorption peak around 1000 nm due to Yb³⁺ ion. The lifetime measurement also reveals the energy transfer from Er³⁺ to Yb³⁺ ions. The maximum value of energy transfer efficiency (ETE) and corresponding theoretical internal quantum efficiency are estimated as 74% and 174% respectively.     

Efficient near-infrared to visible and ultraviolet upconversion in polycrystalline BiOCl:Er3+/Yb3+ synthesized at low temperature

Er³⁺/Yb³⁺ co-doped BiOCl poly-crystals were synthesized by the conventional solid state method at 500 °C, which exhibited good crystalline and low phonon energy. Under 980 nm excitation, the samples showed intense red upconversion (UC) luminescence (Er³⁺: ⁴F_9/2→⁴I_15/2) as well as other four UC emission bands, including ultraviolet (UV) emission at 380 nm, violet emission at 411 nm, green UC emissions at 525 and 545 nm and near-infrared (NIR) emission between 800 and 850 nm, corresponding to the transitions of ⁴G_11/2, ²H_9/2, ²H_11/2, ⁴S_3/2 and ⁴I_9/2→⁴I_15/2 of Er³⁺, respectively. Interestingly, including the violet and green UC emissions, the red one originated a nearly three-photon process in this system, and a possible UC mechanism was proposed for the enhanced red emission.     

1.53 µm luminescence properties of Er3+-doped K–Sr–Al phosphate glasses

Trivalent erbium (Er³⁺)-doped K–Sr–Al phosphate glasses were prepared and studied their spectroscopic properties as a function of Er₂O₃ concentration. Judd–Ofelt analysis has been carried out for 1.0 mol% Er₂O₃-doped phosphate glass and in turn radiative properties have been evaluated for the excited levels of Er³⁺ ion. The radiative lifetime for the ⁴I_13/2 level was found to be higher for the present glass when compared to other Er³⁺-doped glasses. The Er³⁺-doped glasses exhibit intense near infrared emission at 1.53 µm corresponds to ⁴I_13/2→⁴I_15/2 transition as well as green emission at 546 nm corresponding to ⁴S_3/2→⁴I_15/2 under 980 nm and 488 nm excitations, respectively. The emission cross-section spectrum for 1.0 mol% of Er₂O₃-doped glass has been evaluated using McCumber theory. The gain cross-section has been evaluated as a function of population inversion, which revealed that the lasing action would be achieved at 1.53 µm for a population inversion about 40%. Decay curves for the ⁴I_13/2 level were measured and lifetimes have been determined for the studied glasses. The results indicate that the present glasses could be useful for laser as well as optical amplifiers at 1.53 µm.     

Effects of Gd3+ substitution on the structure,photoluminescence, scintillation,and thermometric features of Pr3+:Lu2Zr2O7 phosphors

In this study, it is shown how the photoluminescence, scintillation, and optical thermometric properties are managed via the introduction of Gd³⁺ ions into Pr³⁺:Lu₂Zr₂O₇. Raman spectra validate that partial replacement of Lu³⁺ with Gd³⁺ can promote the phase transition of Lu₂Zr₂O₇ host from the defective fluorite structure to the ordered pyrochlore one. Upon 289 nm excitation, all the samples emit the 483 (³P₀ → ³H₄), 581 (¹D₂ → ³H₄), 611 (³P₀ → ³H₆), 636 (³P₀ → ³F₂), and 714 nm (³P₀ → ³F₄) emissions from Pr³⁺ ions, which are enhanced with the addition of Gd³⁺ ions due to the modification of crystal structure. Dissimilarly, the X-ray excited luminescence spectra consist of a strong emission located at 314 nm from Gd³⁺ ions (⁶P_7/2 → ⁸S_7/2), together with the typical emissions from Pr³⁺ ions, which exhibit different dependences on the Gd³⁺ concentration. When the luminescence intensity ratio between the ³P₀ → ³H₆ (611 nm) and ¹D₂ → ³H₄ (581 nm) transitions is selected for temperature sensing, Pr³⁺:(Lu_0.75Gd_0.25)₂Zr₂O₇ shows the optimal relative sensing sensitivity of 0.78% K⁻¹ at 303 K, which is higher than that of the Gd³⁺-free sample. Therefore, the developed Pr³⁺:(Lu, Gd)₂Zr₂O₇ phosphors have the applicative potential for optical thermometry, X-ray detection, and photodynamic therapy.     

Upconverting luminescence based dual-modal temperature sensing for Yb3+/Er3+/Tm3+: YF3 nanocrystals embedded glass ceramic

Yb³⁺/Er³⁺/Tm³⁺ doped transparent glass ceramic containing orthorhombic YF₃ nanoparticles was successfully synthesized by a melt-quenching method. After glass crystallization, tremendously enhanced (about 5000 times) upconversion luminescence, obvious Start-splitting of emission bands as well as long upconversion lifetimes of Er³⁺/Tm³⁺ confirmed the incorporation of lanthanide activators into precipitated YF₃ crystalline environment with low phonon energy. Furthermore, temperature-dependent upconversion luminescence behaviors of glass ceramic were systematically investigated to explore its possible application as optical thermometric medium. Impressively, both fluorescence intensity ratio of Er³⁺: ²H_11/2 → ⁴I_15/2 transition to Er³⁺: ⁴S_3/2 → ⁴I_15/2 one and fluorescence intensity ratio of Tm³⁺: ³F_2,3 → ³H₆ transition to the combined Tm³⁺: ¹G₄ → ³F₄/Er³⁺: ⁴F_9/2 → ⁴I_15/2 ones were demonstrated to be applicable as temperature probes, enabling dual-modal temperature sensing. Finally, the thermal effect induced by the irradiation of 980 nm laser was found to be negligible in the glass ceramic sample, being beneficial to gain intense and precise probing signal and detect temperature accurately.     

Structural,optical, and spectroscopic properties of Er3+-doped TeO2–ZnO–ZnF2 glass-ceramics

Transparent fluorotellurite glass-ceramics have been obtained by heat treatment of precursor Er-doped TeO₂–ZnO–ZnF₂ glasses. ErF₃ nanocrystals nucleated in the glass-ceramics have a typical size of 45 ± 10 nm. Based on the Judd-Ofelt theory, the main radiative parameters for the ⁴I_13/2 → ⁴I_15/2 transition have been obtained. The split of the absorption and emission bands and the reduction of the Ω₂ parameter, as compared to the glass, confirm the presence of Er³⁺ ions in a crystalline environment in glass-ceramic samples. The analysis of the ⁴I_13/2 decays suggests that a fraction of Er³⁺ ions remains in a glass environment while the rest forms nanocrystals. For the glass-ceramics, intense red and green upconversion emissions were observed with an enhancement of the ⁴F_9/2 → ⁴I_15/2 red one compared to the glass sample. The temporal evolution of the red emission together with the excitation upconversion spectra suggests that energy transfer processes are responsible for the enhancement of the red emission.     

Enhancement of up-conversion emission and emerging cool white light emission in co-doped Yb3+/ Er3+: Li2O-LiF-B2O3-ZnO glasses for photonic applications

A series of co-doped (Yb³⁺/Er³⁺): Li₂O-LiF-B₂O₃-ZnO glasses were prepared by standard melt quenching technique. Structural and morphological studies were carried out by XRD and FESEM. Phonon energy dynamics have been clearly elucidated by Laser Raman analysis. The pertinent absorption bands were observed in optical absorption spectra of singly doped and co-doped Yb³⁺/Er³⁺: LBZ glasses. We have been observed a strong up-conversion red emission pertaining to Er³⁺ ions at 1.0 mol% under the excitation of 980 nm. However, the up-conversion and down conversion (1.53 µm) emission intensities were remarkably enhanced with the addition of Yb³⁺ ions to Er³⁺: LBZ glasses due to energy transfer from Yb³⁺ to Er³⁺. Up-conversion emission spectra of co-doped (Yb³⁺/Er³⁺): LBZ glasses exhibits three strong emissions at 480 nm, 541 nm and 610 nm which are assigned with corresponding electronic transitions of ²H_9/2 → ⁴I_15/2, ⁴S_3/2 → ⁴I_15/2 and ⁴F_9/2 → ⁴I_15/2 respectively. Consequently, the green to red ratio values (G/R) also supports the strong up-conversion emission. The Commission International de E′clairage coordinates and correlated color temperatures (CCT) were calculated from their up-conversion emission spectra of co-doped (Yb³⁺/Er³⁺): LBZ glasses. The obtained chromaticity coordinates for optimized glass (0.332, 0.337) with CCT value at 5520 K are very close to the standard white colorimetric point in cool white region. These results could be suggested that the obtained co-doped (Yb³⁺/Er³⁺): LBZ glasses are promising candidates for w-LEDs applications.     

Realizing particle population inversion of 2.7 μm emission in heavy Er3+/Pr3+ co-doped low hydroxyl fluorotellurite glass for mid-infrared laser

In this work, the population bottleneck of Er³⁺: ⁴I_11/2 → ⁴I_13/2 was overcome for the first time in heavy Er³⁺/Pr³⁺ co-doped TeO₂–BaF₂–La₂O₃–LaF₃ (TBLL) low hydroxyl fluorotellurite glasses. Infrared emission spectra and fluorescence lifetime decay curves reveal that Pr³⁺ ions could deplete the electrons from the Er³⁺: ⁴I_13/2 level faster than those from the Er³⁺: ⁴I_11/2 under 980 nm excitation. Specifically, the energy transfer (ET) efficiency of the Er³⁺: ⁴I_13/2 → Pr³⁺: ³F_3,4 process (ET1) reached 96.27%, while that of the Er³⁺: ⁴I_11/2 → Pr³⁺: ¹G₄ process (ET2) is only 2.17% in the Er³⁺/Pr³⁺ co-doped glass. Additionally, the energy transfer mechanism of Er³⁺ and Pr³⁺ ions was investigated using the Dexter theory, where the energy transfer microscopic parameters C_D-A are 13.21 × 10⁻⁴⁰ cm⁶/s and 0.89 × 10⁻⁴⁰ cm⁶/s for the ET1 and ET2 processes, respectively. Finally, a numerical simulations laser model was developed to discuss the laser properties of the Er³⁺/Pr³⁺ co-doped TBLL fibers. The simulation results indicate that a 2.7 μm laser with a maximum output power of 2.26 W and slope efficiency of 13.89% could be achieved when the fiber background loss is reduced to 0.5 dB/m. The above results suggest that the Er³⁺/Pr³⁺ co-doped TBLL glass has great potential applications in mid-infrared fiber lasers.     

Erbium-Doped Fluoroborate Glasses for Near Infrared Broadband Amplifiers

Erbium (Er³⁺)-doped alkali lead tellurofluoroborate (RLTB) glasses were prepared and characterized systematically through optical absorption and emission measurements. The emission spectra in the range 450–900 and 1400–1800 nm were recorded by exciting the samples with 532 nm (Nd : YVO₄ crystal) and 514.5 nm (Ar⁺ laser), respectively. Applying Judd–Ofelt analysis, the intensity parameters have been determined using experimental oscillator strengths of absorption bands. From the Judd–Ofelt intensity parameters, some important fluorescence properties such as spontaneous transition probabilities, radiative lifetimes and luminescence branching ratios for the ⁴S_3/2→⁴I_15/2 (0.55 μm), ⁴S_3/2→⁴I_13/2 (0.85 μm), and ⁴I_13/2→⁴I_15/2 (1.54 μm) emission transitions of Er³⁺ ion in RLTB glasses have been calculated. The continuous pumping of the samples results in fast nonradiative decay through ²H_11/2→⁴F_9/2 (~3500 cm⁻¹) transition, which in turn causes the population of Er³⁺ ions from ²H_11/2 state to the higher ⁴F_3/2 state. The emission cross sections determined for the ⁴I_13/2→⁴I_15/2 (1.54 μm) transition using the McCumber theory are in good agreement with the values obtained from the Judd–Ofelt analysis. From evaluated radiative parameters, it is suggested that these RLTB glasses are more suitable candidates for 0.85 and 1.54 μm broadband optical amplifiers.     

Optical temperature sensor based on upconversion luminescence of Er3+ doped GdTaO4 phosphors

For the development of optical temperature sensor, a series of GdTaO₄ phosphors with various Er³⁺-doping concentrations (0, 1, 5, 10, 25, 35, 50 mol%) were synthesized by a solid-state reaction method. The monoclinic crystalline structure of the prepared samples was determined by X-ray diffraction (XRD). Under excitations of 980 and 1550 nm lasers, the multi-photon-excited green and red upconversion (UC) luminescence emissions of Er³⁺ were studied, and the critical quenching concentration of Er³⁺-doped GdTaO₄ phosphor was derived to be 25 mol%. By changing the pump power of laser, it was found that the two-photon and three-photon population processes happened for the UC emissions of Er³⁺-doped GdTaO₄ phosphors excited by 980 and 1550 nm lasers, respectively. Furthermore, based on the change of thermo-responsive green UC luminescence intensity corresponding to the ²H_11/2 → ⁴I_15/2 and ⁴S_3/2 → ⁴I_15/2 transitions of Er³⁺ with temperature, the optical temperature sensing properties of Er³⁺-doped GdTaO₄ phosphor were investigated under excitations of 980 and 1550 nm lasers by using the fluorescence intensity ratio (FIR) technique. It was obtained that the maximum absolute sensitivity (S_A) and relative sensitivity (S_R) of Er³⁺-doped GdTaO₄ phosphors are as high as 0.0041 K⁻¹ at 475 K and 0.0112 K⁻¹ at 293 K, respectively. These significant results suggest that the Er³⁺-doped GdTaO₄ phosphors are a promising candidate for optical temperature sensor.     

Design and preparation of white light emission from up-conversion transitions in Er3+/Tm3+/Yb3+ co-doped cubic zirconia single crystals

High-quality cubic YSZ crystals were designed with various contents of Er³⁺, Tm³⁺ and Yb³⁺ to produce white light emission, and grown by the optical floating zone method. The up-conversion luminescence spectra of the crystals under 980 nm laser irradiation show three distinct groups of emission peaks at ∼473 nm (blue) generated by the Tm^{3+ 1}G₄→³H₆ transition, 531 and 547 nm (green) from the Er^{3+ 2}H_11/2 → ⁴I_15/2 and ⁴S_3/2 → ⁴I_15/2 transitions, and 640 and 662 nm (red) from the Er^{3+ 4}F_9/2 → ⁴I_15/2 transition. The optical power curve obtained by plotting the up-conversion luminescence intensity against the laser power shows that the blue emission involves a three-photon process, whilst both the green and red emissions are the results of two-photon processes. Overall white light emission was observed with the crystal prepared with 0.05 mol% Er₂O₃, 0.5 mol% Tm₂O₃ and 2.0 mol% Yb₂O₃, and this crystal is suitable for use in highly efficient white light emission devices.     

Dual-mode dichromatic SrBi4Ti4O15: Er3+ emitting phosphor for anti-counterfeiting application

Fluorescent materials have been widely used for anti-counterfeiting of important documents and currencies, wherein their anti-counterfeit abilities could be improved through multi-mode excitation. Herein, dual-mode-excited double-colour-emitting Er³⁺doped SrBi₄Ti₄O₁₅ up-conversion (UC) phosphors (SBTO: Er³⁺) were synthesised, and their UC spectra included green (2H11/2/4S3/2 → 4I15/2) and red (4F9/2 → 4I15/2) emissions from Er3+ ions under 980 or 1550 nm excitation. However, the green emission colour of phosphors was independent of dopant concentration under 980 nm laser irradiation; whereas the final emission colour was dominated by red emission and significantly affected by contents of Er3+ under 1550 nm excitation. These observations demonstrated potential application in dual-mode double-colour anti-counterfeiting. The possible UC mechanisms and emission characteristics of the phosphors using different 980 and 1550 nm irradiation source were contrastively investigated, and some fluorescent security patterns were also designed to demonstrate the potential applications in anti-counterfeiting and concealing important information.     

Thermochromic Pr3+ doped CaMoO4 phosphor with diverse thermal responses for temperature sensing

CaMoO₄:Pr³⁺ thermochromic phosphors with diverse thermal responses for temperature sensing were prepared by the traditional solid-phase reaction method. The typical CaMoO₄:Pr³⁺ had scheelite structure belonging to tetragonal crystal system and space group of I4₁/a (88). Pr³⁺ ions can be easily substituted for Ca²⁺ ions of host CaMoO₄ because of similar ionic radius. CaMoO₄: 1.5% Pr³⁺ have the block structure with mean size of 6.84 μm. The E_g (∼3.93 eV) value of pure CaMoO₄ is bigger than that (∼3.65 eV) of CaMoO₄: 1.5%Pr³⁺, attributing to the existence of intermediate defect energy levels. Appropriate Pr³⁺ doping concentration is 1.5%, and the concentration quenching phenomenon can be explained by the concrete electric multipole type of d-d interaction. The emission peak at ∼605 nm from ¹D₂→³H₄ transition have a good thermal stability of 99.452%@423 K, while the wide band centered at ∼490 nm from ³T_1,2 → ¹A₁ transition in the MoO₄²⁻ complex and ³P₀→³H₄ transition in Pr³⁺ have a poor thermal stability of 27.572%@423 K. Calculated activation energy is 0.239 eV. Temperature-dependent FIR for optical thermometry was constructed due to their diverse thermal responses. CaMoO₄: Pr³⁺ phosphor had good relative sensitivities of 2.216%, 0.969% and 0.932% based on FIR of I_{605 nm}/I_{490 nm} with Boltzmann distribution, modified Boltzmann distribution and exponential equation fitting. Thermochromic behavior and thermal quenching mechanism are investigated. The obtained relative sensitivity is better than that of most phosphors, implying that CaMoO₄: Pr³⁺ has a potential for application in optical thermometry.