Energy transfer and luminescent properties of Tb3+ and Tb3+, Yb3+ doped CNGG phosphors

In this work,calcium niobium gallium garnet(Ca₃ Nb_1.6875Ga_3.1875O₁₂-CNGG) ceramic samples singledoped with Tb³⁺ and co-doped with Tb³⁺ and Yb³⁺ ions were sintered by the solid-state reaction method.The structural characterization of the samples was carried out by X-ray diffraction measurements.The optimal concentration of Tb³⁺ ions corresponding to the maximum luminescence in the green spectral range in CNGG:...     

Up-conversion luminescence of Er~（3＋）-doped and Yb~（3＋）/Er~（3＋） co-doped 12CaO·7Al_2O_3 poly-crystals

The optical properties of Er3+-doped and Yb3+/Er3+ co-doped 12CaO·7Al2O3 (C12A7) poly-crystals, synthesized by high temperature solid state method, were investigated in detail. For Er3+-doped and Yb3+/Er3+ co-doped C12A7 poly-crystals, two main emission bands centered around 530/550 nm (green) and 660 nm (red) were observed under 980 nm diode laser excitation via an up-conversion process. The intensity of green up-conversion emission had a strong increase in Er3+ (1.0 mol.%, 1.5 mol.%, 3.0 mol.%), and the intensity ratio of red to green up-conversion emission had an increase in Yb3+ (1.0 mol.%, 2.0 mol.%, 10. 0 mol.%)/Er3+ (fixed at 1.0 mol.%). This detailed study of the up-conversion processes allowed us to identify the dominant up-conversion mechanisms in Er3+-doped and Yb3+/Er3+ co-doped C12A7 poly-crystals.     

Tm^3＋-doped tellurite glass with Yb^3＋ energy sensitized for broadband amplifier at 1400-1700 nm bands

A kind of novel experiment was disclosed as it possessed two bands of fluorescence emission at 1.4 and 1.6 μm, which were perfectly complimentary to the current C band of optic communication. The fluorescence was based on energy transfer and up-conversion processes between Tm^3＋ and Yb^3＋ under direct pumping of 975 nm LD. The spectra and lifetimes of Tm^3＋ fluorescence in the tellurite glass were described. The corresponding fluorescence characteristics and energy migration process were analyzed by the method of lifetime and intensity comparison. The mechanism of the up-conversion based IR fluorescence was presented upon analyzing the multi-photon pumping process. The potential advantages of Tm^3＋/Yb^3＋ co-doped tellurite glass as amplifier material were concluded.     

Y4GeO8:Er3+,Yb3+ up-conversion phosphors for optical temperature sensor based on FIR technique

Herein, we reported novel Y₄GeO₈:Er³⁺,Yb³⁺ phosphors elaborated via conventional solid-state reaction, and we further explored their properties as optical thermometer by using fluorescence intensity ratio (FIR) method complemented by detailed analysis on crystal structure, up-conversion luminescence and energy transfer from Yb³⁺ to Er³⁺. Upon 980 nm laser excitation, Y₄GeO₈:Er³⁺,Yb³⁺ phosphors present 525, 547 and 659 nm emission bands assigned to the characteristic transitions of Er³⁺. Furthermore, Y₄GeO₈:Er³⁺,Yb³⁺ samples show outstanding temperature sensing performances. To be specific, the minimal temperature resolution is 0.03 K (303 K), and the relative sensitivity of FIR can be up to 1.152%/K (303 K). Hence, Y₄GeO₈:Er³⁺,Yb³⁺ phosphors can be possible candidates for thermometry devices.     

Nd~(3+)/Yb~(3+) co-doped mid-infrared luminescence fluorobromide glass with energy transfer and zero-thermal-quenching IR emission

Nd~(3+)/Yb~(3+) co-doped fluorobromide glass samples were prepared by melt quenching.The mid-infrared(MIR) luminescence of the Nd~(3+)/Yb~(3+) co-doped fluorobromide glass was investigated by Br-doping reduces the phonon state density of the matrix.The 3.9 μm MIR luminescence of the samples excited at 793 and 980 nm pump excitation was investigated in detail.There is an effective mutual energy transfer process between Nd~(3+) and Yb~(3+).It is proved under 793 nm excitation that the luminescence of Nd~(3+)at 3.9 μm is reduced by effective energy transfer from,Nd~(3+):~2 H_(11/2)→Yb~(3+):~2 F_(5/2),At the same time,it is proved that the effective energy transfer from Yb~(3+):~2 F_(5/2)→Nd~(3+):2 H_(11/2) under the excitation of 980 nm enhances the luminescence of Nd~(3+) at 3.9 μm.In addition,it is found that the samples still have good infrared(IR) luminescent properties when the temperature changes.The emission cross-sectional area and the absorption cross-sectional area are σ_(em)(3.87 × 10~(-20) cm~2) and σ_(abs)(4.25×10~(-20) cm~2).The fluorescence decay characteristics of the sample at 3.9 μm at the ~2 H_(11/2) level were investigated and the fluorescence lifetime was calculated.The gain performance of the sample was calculated and analyzed,which can reach 4.25 × 10~(-20) cm~2.Those results prove that Nd~(3+)/Yb~(3+)co-doped fluorobromide glass is the potential mid-infrared laser gain material.     

Selecting nitride host for Yb3+ toward near-infrared emission with low-energy charge transfer band

Yb³⁺-doped phosphors have characteristic near-infrared (NIR) emissions, but their applications in phosphor-converted light-emitting-diodes (pc-LEDs) and Si solar cells are limited due to their mismatching excitation spectra. Here, we selected nitride La₃Si₆N₁₁ (LSN) as host material to achieve Yb³⁺ NIR emission upon low-energy charge transfer (CT) excitation. The obtained phosphor LSN:Yb³⁺ has a broad CT excitation band ranging from 250 to 500 nm and narrowband NIR emissions ranging from 950 to 1100 nm centered at 983 nm. On the basis of spectral data, the vacuum referred binding energies (VRBE) schemes are constructed to locate energy levels of all lanthanide ions in LSN. We also fabricated NIR pc-LED device using 395 nm LED chip to demonstrate the potential applications of LSN:Yb³⁺ phosphors.     

Energy transfer process of Nd3+/Ho3+ co-doped fluoride halide glasses with anion substituted multi-wavelength tunable mid-infrared luminescence

Ho³⁺ doped ZBLAN glass with 2.0 and 2.9 μm emission was prepared. In order to further improve the luminescence of Ho³⁺, halogen ions (Cl, Br, I) were introduced to reduce the maximum phonon energy and phonon state density of the sample. At the same time, Nd³⁺ was introduced to transfer the energy to Ho³⁺ pumped with a 793 nm laser (Nd³⁺:⁴F_5/2,⁴F_3/2→Ho³⁺:⁵I₆). The effect of different halogen ion on the luminescent properties of the fluoride halide glass was compared. The results show that the luminescent intensity of infrared increases with the introduction of different halogen ions. By comparison, it is found that the sample with I^– has the strongest luminescence of 1064 nm, 2.0 μm and 2.9 μm. This is consistent with the calculated J-O intensity parameters. In addition, the 2.0 and 2.9 μm emission of Ho³⁺ pumped with a 450 nm laser will not disappear. A mid-infrared sample with multi-wavelength excitation and multi-wavelength emission can be obtained. Nd³⁺/Ho³⁺ co-doped fluoride halide glasses with 1064 nm, 2.0 μm and 2.9 μm luminescence were prepared by melt quenching method. The luminescent mechanism and the energy transfer process between the two ions of Nd³⁺/Ho³⁺ co-doped fluoride halide glass were studied. The J-O parameters, luminescence lifetime and absorption emission cross-sectional area of Ho³⁺ and Nd³⁺ were calculated, respectively. It is found that the value of Ω₂ in the glass matrix increases with the introduction of different halogen ions, while Ω₄ and Ω₆ do not change obviously in different glass compositions. This is because the environment of the crystal field around the rare earth ions changes. The crystal phase and phonon energy of the sample were analyzed by X-ray diffraction pattern and a Fourier transform infrared spectrometer, respectively. Based on the above spectra and data (phonon energy is 634.71 cm⁻¹), it can be predicted that Nd³⁺/Ho³⁺ co-doped fluoride halide glass is a potential mid-infrared luminescent material.     

Gd3+ ion induced UV upconversion emission and temperature sensing in Tm3+/Yb3+:Y2O3 phosphor

Cubic phase Tm³⁺/Yb³⁺:Y₂O₃ and Tm³⁺/Yb³⁺/Gd³⁺:Y₂O₃ phosphors were prepared by low temperature combustion technique for upconversion emission in UV-visible range.The 980 nm excitation has generated UV emission at 314 nm in tridoped phosphor due to the energy transfer from Tm³⁺ to Gd³⁺ion.Characteristic emission bands from Tm³⁺ are also observed in both the phosphors....     

Effect of BaF2 addition on luminescence properties of Er3+/Yb3+ co-doped phosphate glasses

Er~(3+)/Yb~(3+) co-doped phosphate glasses(P_2O_5-Al_2O_3-BaO-BaF_2-K_2O-Er_2O_3-Yb_2O_3) with varying BaF_2 content,were prepared by a conventional melt quenching technique and their spectroscopic properties were examined through the Raman, absorption, emission and decay measurements. Raman spectra(350-1400 cm~(-1)) of the Er~(3+)/Yb~(3+) co-doped phosphate glasses with varying BaF_2 content, were recorded upon laser excitation at 785 nm. Near infrared luminescence spectra were measured in the1400-1600 nm region under 970 nm diode laser excitation and characteristic band was observed at1533 nm corresponding to ~4Ⅰ_(13/2)→~4Ⅰ_(15/2) transition of Er~(3+) ion. The decay curves for the ~4Ⅰ_(13/2) level of Er~(3+)ion, were measured and the lifetime is found to decrease from 7.94 to 7.70 ms when BaF_2 content increases from 0 to 8 mol% and then increases up to 7.83 ms with further increase in BaF_2 content(12 mol%). The emission cross-section.lifetime and figure of merit for the ~4Ⅰ_(13/2)→~4Ⅰ_(15/2) transition of Er~(3+) ion were evaluated and compared to the other host matrices. The upconversion luminescence was measured and intense red emission was observed for all the studied samples.     

White up-conversion luminescence and highly-sensitive optical temperature sensing in Na3La(VO4)2:Yb,Er,Tm,Ho phosphors

In this work,tunable white up-conversion luminescence was achieved in the Yb³⁺,Er³⁺,Tm³⁺,Ho³⁺ codoped Na₃La(VO₄)₂ phosphors under 980 nm excitation.The emissions of three primary colors are mainly attributed to the ²H_11/2/⁴S_3/2→⁴I_15/2 transitions of Er³⁺,¹G₄→³H₆ transition of Tm³⁺,and_5...     

Up-conversion of Er3＋/yb3＋ co-doped transparent glass-ceramics containing Ba2LaF7 nanocrystals

The up-conversion of Er3+/Yb3+co-doped transparent glass-ceramics 50SiO2-10AlF3-5TiO2-30BaF2-4LaF3-0.5ErF3-0.5YbF3 containing Ba2 LaF7 nanocrystals under the changing of heat treatment temperature and time were investigated.The Ba2 LaF7 nanocrystals precipitated from the glass matrix was confirmed by X-ray diffraction(XRD).The structural investigation carried out by XRD and transmission electron microscopy(TEM) evidenced the formation of cubic Ba2 LaF7 nanocrystals with crystal size of about 14 nm.Comparing with the samples before heat treatment,the high efficiency up-conversion emission of Er3+/Yb3+co-doped samples was observed in the glass-ceramics under 980 nm laser diode excitation.The increase in red emission intensity bands was stronger than the green bands when the crystal size increased.The mechanism for the up-conversion process in the glass-ceramics and the reasons for the increase of Er3+/Yb3+co-doped up-conversion intensity after heat treatment were discussed.     

Size dependence of up-conversion luminescence of NaYF4:Yb3+/Tm3+

Tm³⁺/Yb³⁺ codoped NaYF₄ microcrystals were synthesized using a hydrothermal method. The bright upconversion light was observed under 980 nm excitation. The upconversion luminescence was systematically investigated at different Yb³⁺ concentrations and different reaction temperatures and time. The sample with 60% Yb³⁺ concentration and reacting at 180 °C for 24 h possessed the highest luminescent efficiency. The higher luminescent efficiency was contributed to a large surface area. The large surface area induced the large vibration mode by absorbed H₂O and CO₂. The larger vibration mode could enhance the energy transfer efficiency from the excited Yb³⁺ to Tm³⁺ by the process of phonon assisted energy transfer.     

Effects of Bi3+ on down-/up-conversion luminescence,temperature sensing and optical transition properties of Bi3+/Er3+ co-doped YNbO4 phosphors

A series of YNbO₄:Bi³⁺ and YNbO₄:Bi³⁺/Er³⁺ phosphors were prepared by a conventional high temperature solid–state reaction method. The results of XRD and Rietveld refinement confirm that monoclinic phase YNbO₄ samples are achieved. The down-/up-conversion luminescence of Er³⁺ ions was investigated under the excitation of ultraviolet light (327 nm) and near infrared light (980 nm). Under 327 nm excitation, broad visible emission band from Bi³⁺ ions and characteristic green emission peaks from Er³⁺ ions are simultaneously observed, while only strong green emissions from Er³⁺ ions are detected upon excitation of 980 nm. Remarkable emission enhancement is observed in down-/up-conversion luminescence processes by introducing Bi³⁺ ions into Er³⁺-doped YNbO₄ phosphors. Pumped current versus up-conversion emission intensity study shows that two-photon processes are responsible for both the green and the red up-conversion emissions of Er³⁺ ion. Through the study of the temperature sensing property of Er³⁺ ion, it is affirmed that the temperature sensitivity is sensitive to the doping concentration of Bi³⁺ ions. By comparing the experimental values of the radiative transition rate ratio of the two green emission levels of Er³⁺ ions and the theoretical values calculated by Judd-Ofelt (J-O) theory, it is concluded that the temperature sensing property of Er³⁺ ions is greatly affected by the energy level splitting.     

Tm3+-doped tellurite glass with Yb3+ energy sensitized for broadband amplifier at 1400-1700 nm bands

A kind of novel experiment was disclosed as it possessed two bands of fluorescence emission at 1.4 and 1.6 μm, which were per-fectly complimentary to the current C band of optic communication. The fluorescence was based on energy transfer and up-conversion proc-esses between Tm3+ and Yb3+ under direct pumping of 975 nm LD. The spectra and lifetimes of Tm3+ fluorescence in the tellurite glass were described. The corresponding fluorescence characteristics and energy migration process were analyzed by the method of lifetime and inten-sity comparison. The mechanism of the up-conversion based IR fluorescence was presented upon analyzing the multi-photon pumping proc-ess. The potential advantages of Tm3+/Yb3+ co-doped tellurite glass as amplifier material were concluded.     

Broadband downconversion in YVO4：Tm3＋,Yb3＋ phosphors

An efficient near-infrared (NIR) downconversion (DC) by converting broadband ultraviolet (UV) into NIR was demonstrated in YVO4:Tm3+,Yb3+ phosphors. The phosphors were extensively characterized using various methods such as X-ray diffraction, photoluminescence excitation, photoluminescence spectra and decay lifetime to provide supporting evidence for DC process. Upon UV light varying from 260 to 350 nm or blue light (473 nm) excitation, an intense NIR emission of Yb3+ corresponding to transition of 2F5/2→2F7/2 peaking at 985 nm was generated. The visible emission, the NIR mission and the decay lifetime of the phosphors of various Yb3+ concentrations were investigated. Experimental results showed that the energy transfer from vanadate group to Yb3+ via Tm3+ was very efficient. Application of the broadband DC YVO4:Tm3+,Yb3+ phosphors might greatly enhance response of siliconbased solar cells.     

Multicolor luminescence of hexagonal NaYF4:Yb3+/Ho3+/Ce3+ microcrystals with tunable morphology under 940 nm excitation for temperature-responsive anti-counterfeiting

In this study, the hexagonal NaYF₄:Yb³⁺/Ho³⁺/Ce³⁺ microcrystals were synthesized controllably, and upconversion luminescence excited at 940 nm and its application in temperature-responsive anti-counterfeiting are reported. It is clarified that the Ln³⁺ (Ln = Y + Yb + Ho + Ce) density ratio of bottom plane to side plane in the unit cell can be regulated by Ce³⁺ doping. It is also proved that the energy transfer of Yb³⁺ to Ho³⁺ is responsible for the activation of Ho³⁺ under 940 nm excitation, while the cross relaxation between Ho³⁺ and Ce³⁺ participates in the redistribution of electron population of ⁵S₂/⁵F₄ and ⁵F₅ levels. Both theory and experiment confirm that the intensity ratio of red to green emission (I_R/I_G) as a function of temperature as an independent variable has good linear characteristics in the temperature range of 300–500 K. Due to the good responsiveness of multicolor luminescence to temperature, the hexagonal NaYF₄:Yb³⁺/Ho³⁺/Ce³⁺ with tunable morphology is a promising candidate for advanced temperature-responsive upconversion anti-counterfeiting. Our results provide a new pathway for the controllable synthesis of hexagonal NaYF₄ microcrystals as well as the regulation of upconversion luminescence that is excited by wavelengths other than 980 nm and its application in anti-counterfeiting.     

Spectral Properties and Upconversion Luminescence of Er^3＋, yb^3＋： BaWO4 Crystal

The optical quality of Er^3＋, yb^3＋： BaWO4 crystal was gown by Czochralski method. Absorption spectra were measured and energy levels were assigned. According to Judd-Ofelt theory, the spectral strength parameters of Er^3＋ ion were fitted to beΩ2 =0.3926 x 10^-20 cm^2, Ω4 =0.0721×10^-20 cm^2, Ω6 =0.0028 ×10.20 cm^2. Emission peaks centered at around 523,544 and 670 nm were observed under 334 nm He-Cd laser excitation and emission peaks centered at 1001 and 1534 nm were detected under 976 nm laser excitation. Strong green emission was also observed when the crystal was pumped with 808 nm and 976 nm laser. The mechanisms of frequency upconversion and sensitization were analyzed.     

A NIR to NIR rechargeable long persistent luminescence phosphor Ca2Ga2GeO7:Yb3+,Tb3+

Near infrared to near infrared (NIR–NIR) photo-stimulated persistent luminescence (PSPL) has shown excellent potential in high-resolution bioimaging for deep tissues. However, the PSPL in NIR-Ⅱ region (900–1700 nm) is still lacking. In this work, Ca₂Ga₂GeO₇:Yb³⁺,Tb³⁺ (CGGYT) phosphor with unique low-dimensional crystal structure was synthesized by high-temperature solid–state reaction. Thanks to the carriers transferring from deep traps to shallow ones induced by low energy light, the 978 nm PSPL originating from ²F_5/2 to ²F_7/2 transition of Yb³⁺ induced by multimode stimulating (980 nm or WLED) is successfully realized after pre-excited by UV lamp. The NIR PSPL of the specimen can be repeatedly stimulated after placed in dark for 12 h. Moreover, the results indicate that codoping with Tb³⁺ can significantly enhance the NIR-II PSPL owing to the quantum cutting persistent energy transfer (QC PET) from Tb³⁺ to Yb³⁺. Our study points to a new direction for the future development of multimode PSPL materials for bioimaging or multimode optical storage applications.     

Photoluminescence studies of Eu2+-Yb3+ co-doped BaMgAl10O17 phosphor synthesized by the combustion method

BaMgAl10O17:Eu2+,Yb3+ was investigated as a possible quantum cutting system to enhance solar cells efficiency. Phosphors were synthesized by combustion method and composed of nanorods. Photoluminescence spectra showed that Eu in the sample was reduced to bi-valence while Yb remained trivalence. Through a cooperative energy transfer process, the obtained powders exhibited both blue emission of Eu2+ (around 450 nm) and near infrared emission of Yb3+ (around 1020 nm) under broad band excitation (250-410 nm) originating from 4f→5d transition of Eu2+. Energy transfer phenomenon between the sensitizer Eu2+ and the activator Yb3+ was investigated via the lumines-cent spectra and the decay curves of Eu2+ with different Yb3+ concentrations. Results indicated that energy transfer efficiency from Eu2+ to Yb3+ was not high. The poor efficiency can be explained by the long distance between rare earth ions.     

Synthesis of NaYF4:20% Yb3+,2% Er3+,2% Ce3+@NaYF4 nanorods and their size dependent uptake efficiency under flow condition

Lanthanide doped fluorescent nanoparticles have gained considerable attention in biomedical applications. However, the low uptake efficiency of nanoparticles by cells has limited their applications. In this work, we demonstrate how the uptake efficiency is affected by the size of nanoparticles under flow conditions. Using the same size NaYF₄:20% Yb³⁺,2% Er³⁺,2% Ce³⁺ (the contents of rare earths elements are in molar fraction) nanoparticles as core, NaYF₄:20% Yb³⁺,2% Er³⁺,2% Ce³⁺@NaYF₄ core–shell structured nanorods (NRs) with different sizes of 60–224 nm were synthesized by thermal decomposition and hot injection method. Under excitation at 980 nm, a strong upconversion green emission (541 nm, ²H_11/2 → ⁴I_15/2 of Er³⁺) is observed for all samples. The emission intensity for each size nanorod was calibrated and is found to depend on the width of NRs. Under flow conditions, the nanorods with 96 nm show a maximum uptake efficiency by endothelial cells. This work demonstrates the importance of optimizing the size for improving the uptake efficiency of lanthanide-doped nanoparticles.