Photoluminescence of TiO2 films co-doped with Tb/ Gdand energy transfer from TiO2/Gd to Tb ions

Nanometer TiO₂ thin films doped with different concentration of Tb were prepared by sol-gel method and characterized by X-ray diffraction (XRD), thermogravimetry-differential thermal analysis (TG-DTA), transmission electron microscopy (TEM) and photoluminescence (PL) spectroscopy. XRD results show preferentially oriented (101) anatase films. TEM image indicates that the TiO₂ films consist of TiO₂ grains with diameter about 15 nm. Under room temperature, strong visible luminescence of Tb³⁺ ions due to intra-4f shell transitions are obtained and the PL intensity is found to have a well matching relation with the doping concentration of Tb³⁺ ions. Concentration quenching of PL occurs when Tb³⁺ concentration exceeds a certain value (9.2 mol%). Furthermore, the luminescence intensity is improved obviously after co-doping with Gd³⁺ ions because of the sensitization effects of Gd³⁺ ions to Tb³⁺ ions in TiO₂ system. The energy transfer mechanism from TiO₂ and Gd³⁺ ions to Tb³⁺ ions was proposed.     

Thermally stable luminescence and energy transfer in Ce, Mn doped Sr2Mg(BO3)2 phosphor

Sr₂Mg(BO₃)₂:Ce³⁺,Li⁺ and Sr₂Mg(BO₃)₂:Ce³⁺,Li⁺,Mn²⁺ phosphors have been synthesized by conventional solid state reaction technology at 900 °C for 12 h in reducing atmosphere. The phase purity, photoluminescence (PL) properties, thermal stability, energy transfer and luminescent decay curves have been investigated. Sr₂Mg(BO₃)₂:Ce³⁺,Li⁺,Mn²⁺ phosphors show blue and deep-red¹ emission bands. The deep-red emission band is attributed to the energy transfer from Ce³⁺ to Mn²⁺. The fluorescence lifetimes of Ce³⁺ in co-doped sample are shorter than that in single doped one, which confirms that the energy transfer takes place. The phosphors have weak thermal quenching. The luminescence properties of Sr₂Mg(BO₃)₂:Ce³⁺,Li⁺,Mn²⁺ make the phosphor a new bicolor emitting material.     

Energy transfer processes in Ce and Tb co-doped Ln2Si2O7 (Ln = Y, Gd)

The Ce³⁺ and Tb³⁺ co-doped Ln₂Si₂O₇ (Ln = Y, Gd) samples were prepared by sol-gel method. Structure characterization of the phosphor was carried out by X-ray diffraction. The luminescence properties of samples were analyzed by measuring the excitation and emission spectra. It was observed that excitation energy can transfer mutually between Ce³⁺ and Tb³⁺ in GPS: Ce³⁺, Tb³⁺ samples, while in Y₂Si₂O₇ :Ce³⁺, Tb³⁺ samples the energy transfer only progresses from Ce³⁺ to Tb³⁺. Based on the energy level diagrams of respective Ce³⁺, Tb³⁺ and Gd³⁺ ion, the detailed pathways for energy transfer are explained.     

Mid-infrared luminescence and energy transfer of Tm/Yb doped fluorophosphate glass

Tm³⁺/Yb³⁺-codoped fluorophosphate glass is prepared by conventional melt-quenching method and the thermal stability of the glass is analyzed. The Judd–Ofelt parameters, radiation emission rates, radiative lifetime and branching ratios of prepared samples are calculated based on the absorption spectra. Upon excitation of a conventional 980 nm laser diode, 1.8 μm emission is obtained from Yb³⁺/Tm³⁺ codoped fluorophosphate. Additionally, the energy transfer between Yb³⁺ and Tm³⁺ ions are quantitatively analyzed. Hence, this Yb³⁺/Tm³⁺ codoped fluorophosphate glass possessing high energy transfer efficiency and excellent thermal stability is a good candidate for efficient 1.8 μm laser.     

Optical properties of the Tm and energy transfer between Tm→Pr ions in P2O5-CaO-SrO-BaO phosphate glass

A P₂O₅-CaO-SrO-BaO phosphate glass doped with Tm³⁺ and glasses doped with (Tm³⁺, Pr³⁺) were used for this study. The photo-luminescence behaviors of Tm³⁺ and Pr³⁺ in phosphate glass were investigated by absorption, excitation and emission spectroscopy. The energy transfer between Tm³⁺ and Pr³⁺ in phosphate glasses (which exhibit a variety of transfer efficiencies) was studied. The experimental quantum efficiencies of the luminescence of Tm³⁺ η₀ and (Tm³⁺, Pr³⁺) doped phosphate glasses were measured to give η/η₀ = 0.447, 0.305, and 0.179 for (0.4 mol% Pr³⁺, 1.0 mol% Tm³⁺), (0.8%Pr³⁺, 1.0%Tm³⁺) and (1.6 mol% Pr³⁺, 1.0 mol% Tm³⁺), respectively. In order to verify the nature of the ion coupling in our phosphate glass system, we applied the Inokuti-Hirayama model. The non-radiative energy transfer rate from Tm³⁺ to Pr³⁺, transfer efficiencies, and the donor-acceptor distance have been calculated and compared with obtained experimental data. As usual, the efficiency and the probability of energy transfer increase with the concentration of the acceptor.     

Energy transfer in crystalline Er,Yb:Sc2O3

The use of Yb³⁺ as a sensitizer for Er³⁺ doped laser materials is a common technique because of the high Yb³⁺ absorption cross sections. Energy transfer processes from Yb³⁺ to Er³⁺ in Sc₂O₃ are studied by two different methods. Transfer parameters describing the interactions between Er³⁺ and Yb³⁺ ions are obtained on the one hand from the ratio of emitted photons around 1.55 μm by Er³⁺ ions and around 1 μm by Yb³⁺ ions at cw excitation of Yb³⁺, on the other hand by lifetime measurements of Yb³⁺ ions in the codoped samples. Laser experiments are performed to study the suitability of Er³⁺,Yb³⁺:Sc₂O₃ as a laser material. Comparisons with energy transfer in Er³⁺,Yb³⁺:glass are made.     

Upconversion emission from Tm:Yb and Tm:Er:Yb doped Y2SiO5 powders prepared by combustion synthesis

Tm³⁺:Er³⁺:Yb³⁺ doped Y₂SiO₅ powders were prepared by combustion synthesis with estimated as-prepared weight (wt.) % concentrations of 0.25:0.0:2.0, 0.25:0.5:2.0 and 0.25:1.0:2.0, respectively. Blue (Tm³⁺: ¹G₄ → ³H₆), green (Er³⁺: ⁴S_3/2, ²H_11/2 → ⁴I_15/2) and red (Er³⁺: ⁴F_9/2 → ⁴I_15/2) upconversion (UC) emissions were observed under 975 nm infrared diode laser excitation. The UC process took place via energy transfer from Yb³⁺ to Er³⁺ and Tm³⁺ ions. The CIE chromaticity coordinates of Tm³⁺:Er³⁺:Yb³⁺ doped Y₂SiO₅ powders were investigated as a function of the diode laser power and Er³⁺ concentration.     

Efficient Bi → Nd energy transfer in Gd2O3:Bi,Nd

Bi³⁺,Nd³⁺ co-doped Gd₂O₃ were prepared by solid state reaction and the optical properties were investigated. The results show that the near-infrared emission of Nd³⁺ ions is significantly enhanced by the introducing of Bi³⁺ in co-doped samples. An efficient energy transfer from Bi³⁺ to Nd³⁺ corresponds to the near-infrared emission enhancement. The energy transfer efficiency reaches 64.1% for the sample with the strongest near-infrared emission, which has the optimized doping concentrations of 0.5% for Bi³⁺ and 2% for Nd³⁺. The interesting optical properties make Bi³⁺,Nd³⁺ co-doped Gd₂O₃ promising as the luminescent down-conversion layers in front of c-Si solar cells to enhance the performance of the solar cells.     

Enhancement of Er I13/2 population in Y2O3 by energy transfer to Ce

We report measurements of the energy transfer between Er³⁺ and Ce³⁺ in Y₂O₃. The transition between the Er^{3+ 4}I_11/2 and ⁴I_13/2 excited states can be stimulated by energy transfer to Ce³⁺, augmenting the population in the ⁴I_13/2 state at the expense of that in the ⁴I_11/2 state. Experiments were performed on Y₂O₃ planar waveguides doped with 0.2 at.% erbium and 0–0.42 at.% cerium by ion implantation. From measurements of Er³⁺ decay rates as a function of cerium concentration we derive an energy transfer rate constant of 1.3×10⁻¹⁸ cm³/s. The efficiency of the energy transfer amounts to 0.47 at 0.42 at.% cerium. The energy transfer rate constant measured in Y₂O₃ is two times smaller for Er³⁺→Ce³⁺ than that for Er³⁺→Eu³⁺ in the same material.     

Mechanism of energy transfer in Sr2CeO4:Eu phosphor

Blue–white phosphor Sr₂CeO₄ belongs to a particular class of optical materials whose luminescence is governed by optical transitions associated with the electron charge transfer. The originality of its crystallographic structure, a chain-like sequence of luminescent centers, permits an effective transfer of the electronic excitation energy from the host to doped centers. Sr₂CeO₄, рure and doped with Eu³⁺-ions of different concentrations, was synthesized by the Pechini citrate-gel method. The luminescence spectra and luminescence decay curves of Sr₂CeO₄ and Sr₂CeO₄:Eu³⁺ at 300 and 80 K were investigated. The performed experiments revealed the Förster nonradiative energy transfer under the energy migration condition from the crystal host to the doped europium ions.     

Dynamical processes of energy transfer in red emitting phosphor CaMoO4:Sm, Eu

Upon ⁴K_11/2 excitation of Sm³⁺ at 405 nm, the performance of energy transfer from Sm³⁺ to Eu³⁺ in the red emitting phosphor CaMoO₄:Eu³⁺, Sm³⁺ significantly extends its excitation region for better matching the near-UV LED. Photoluminescence spectra indicate that the energy transfer pathway concerns the relaxation from ⁴K_11/2 to ⁴G_5/2 of Sm³⁺ and subsequent transfer to ⁵D₀ of Eu³⁺ rather than ⁵D₁ of Eu³⁺. The fluorescent decay pattern of Sm³⁺⁴G_5/2 level in CaMoO₄:0.5% Sm³⁺, 2% Eu³⁺ is studied at 77 K based on the Inokuti-Hirayama formula, revealing an electronic dipole-dipole interaction between Sm³⁺ and Eu³⁺. The coefficient for the energy transfer is obtained to be 8.5 × 10⁻⁴⁰ s⁻¹ cm⁶. The fluorescence rise and decay pattern of Eu³⁺⁵D₀ level as Sm³⁺ is only excited at 77 K is well described by the dynamical processes of the energy transfer.     

Up-conversion emission in KGd(WO4)2 single crystals triply-doped with Er/Yb/Tm, Tb/Yb/Tm and Pr/Yb/Tm ions

Triply-doped single crystals KGd(WO₄)₂:Er³⁺/Yb³⁺/Tm³⁺, KGd(WO₄)₂:Tb³⁺/Yb³⁺/Tm³⁺ and KGd(WO₄)₂:Pr³⁺/Yb³⁺/Tm³⁺ were grown by the Top Seeded Solution Growth (TSSG) method, with an aim of getting efficient up-converted multicolored luminescence, which subsequently can be used for generation of white light. Such an aim determined the choice of the triply doped compounds: excitation of the Yb³⁺ ions in the infrared spectral region is followed by red, green and blue emission from other dopants. It was shown that all these systems exhibit multicolor up-conversion fluorescence under 980 nm laser irradiation. Detailed spectroscopic studies of their absorption and luminescence spectra were performed. From the analysis of the dependence of the intensity of fluorescence on the excitation power the conclusion was made about significant role played by the host’s conduction band and other possible defects of the KGd(WO₄)₂ crystal lattice in the up-conversion processes.     

Dependence of photoluminescence (PL) emission intensity on Eu and ZnO concentrations in Y2O3:Eu and ZnO·Y2O3:Eu nanophosphors

Y₂O₃:Eu³⁺ and ZnO·Y₂O₃:Eu³⁺ nanophosphor powders with different concentrations of Eu³⁺ ions were synthesized by a sol-gel method and their luminescence properties were investigated. The red photoluminescence (PL) from Eu³⁺ ions with the main emission peak at 612 nm was observed to increase with Eu³⁺ concentration from 0.25 to 0.75 mol% and decreased notably when the concentration was increased to 1 mol%. The decrease in the PL intensity at higher Eu³⁺ concentrations can be associated with concentration quenching effects. The red emission at 612 nm was shown to increase considerable when ZnO nanoparticles were incorporated in Y₂O₃:Eu³⁺ while green emission from ZnO was suppressed. The increase is attributed to energy transfer from ZnO to Eu³⁺.     

Partition, luminescence and energy transfer of Er/Yb ions in oxyfluoride glass ceramic containing CaF2 nano-crystals

A complete spectroscopic investigation of energy transfer processes in oxyfluoride glass ceramics containing CaF₂ nano-crystals doped with various amounts of Er³⁺ and Yb³⁺ was reported. An enhancement of the 1.53 μm emission and infrared to visible up-conversion fluorescence was confirmed experimentally due to efficient non-radiative energy transfer from Yb³⁺ to Er³⁺ ions concentrated in CaF₂ nano-crystals. The efficiency of Yb³⁺ to Er³⁺ energy transfer in excess of 85% was obtained for 0.5 mol% Er³⁺/2.0 mol% Yb³⁺ co-doped glass ceramic. Using rate equation formulism, the coefficient of Yb³⁺ to Er³⁺ energy transfer was determined to be about 3.5 times higher than that of Er³⁺ to Yb³⁺ energy back transfer, which is sufficient to provide high ⁴I_11/2 population of Er³⁺ to improve the fluorescence of the co-doped glass ceramics.     

Photoluminescence and energy transfer investigation from SiO2: Tb,Au inverse opals to rhodamine-B dyes

Energy transfer has attracted extensive attention due to its widespread applications in medical diagnostics, DNA analysis and lighting devices. There are few reports on the energy transfer from rare earth ions to dyes. In the present work, the SiO₂:Tb inverse opals with and without Au nanoparticles were prepared, and the organic rhodamine-B (RhB) dyes were filled into the voids of SiO₂:Tb inverse opals. Non-radiative and radiative energy transfer processes from the SiO₂:Tb inverse opals to the RhB were observed. The influence of Au nanoparticles and photonic band gap on the energy transfer from SiO₂:Tb inverse opals to the RhB was investigated. The Au nanoparticles enhanced energy transfer was observed due to the surface plasmon resonance effects of the Au nanoparticles. When the emission peaks from the SiO₂:Tb inverse opal is overlapped with the photonic band gap, the emission suppression of the SiO₂:Tb inverse opal as well the emission enhancement of the RhB dyes were obtained, which is attributed to improved energy transfer caused by the photonic band gap. The steady state rate equations were used to explain enhancement of energy transfer caused by the photonic band gap.     

Ce to Tb energy transfer in alkaline earth (Ba, Sr or Ca) sulphate phosphors

Energy transfer between Ce³⁺ and Tb³⁺ dopants in alkaline earth (Ba, Sr or Ca) sulphate phosphors is investigated. Among these three phosphors, CaSO₄:Ce³⁺,Tb³⁺ showed maximum Tb³⁺ green emission on excitation with UV light. Photoluminescence measurements reveal that the emission intensity from CaSO₄:Ce³⁺,Tb³⁺ is comparable with that of the commercial green lamp phosphor Ce_0.65Tb_0.35MgAl₁₁O₁₉. Optimum concentrations of dopants in CaSO₄:Ce³⁺,Tb³⁺ are 0.2 mol% each and the optimum sintering treatment following re-crystallisation is 600 °C for 1 h duration. The effect of charge compensator in all the three phosphors is also studied.     

Novel blue-emitting phosphor NaMg4(PO4)3:Eu, Ce with energy transfer

A blue-emitting phosphor of NaMg₄(PO₄)₃:Eu²⁺, Ce³⁺ was prepared by a combustion-assisted synthesis method. The phase formation was confirmed by X-ray powder diffraction measurement. Photoluminescence excitation spectrum measurements show that the phosphor can be excited by near UV light from 230 to 400 nm and presents a dominant luminescence band centered at 424 nm due to the 4f⁶5d¹ → 4f⁷ transition of Eu²⁺ ions at room temperature. Effective energy transfer occurs in Ce³⁺/Eu²⁺ co-doped NaMg₄(PO₄)₃ due to large spectral overlap between the emission of Ce³⁺ and excitation of Eu²⁺. Co-doping of Ce³⁺ enhances the emission intensity of Eu²⁺ greatly by transferring its excitation energy to Eu²⁺, and Ce³⁺ plays a role as a sensitizer. Ce³⁺-Eu²⁺ co-doped NaMg₄(PO₄)₃ powders can possibly be applied as blue phosphors in the fields of lighting and display.     

Structural and vibrational properties of microcrystalline TlM(MoO4)2 (M = Nd, Pr) molybdates

The microcrystalline TlNd(MoO₄)₂ and TlPr(MoO₄)₂ molybdates have been prepared with solid state synthesis on the same synthesis route. The final products have been studied by XRD and SEM. Vibrational properties have been evaluated with Raman spectroscopy. More than 20 narrow Raman lines have been observed in the experimental spectrum of the microcrystals. The most intensive lines related to breathing vibrations of MoO₄ tetrahedra have been found at 904 and ∼930 cm⁻¹. The earlier proposed empirical relation between MoO bond length and stretching mode wavenumber has been tested by the comparative analysis for a suite of sixteen complex molybdates. This well-known relation is found to be unusable for molybdates containing different cations in the crystal lattice.     

Crystal growth and characterization of YAl3(BO3)4 doped with Sc, Ga, Pr, Ho, Tm, Yb

New data on flux growth of mixed crystals (Y,R)(Al,M)₃(BO₃)₄ (R=Pr, Ho, Yb, Tm; M=Sc, Ga) have been obtained. The average R distribution coefficients were found to be 0.53–1.02 for different rare earth elements as well as for scandium and gallium. Two morphological types of (Tm,Y)Al₃(BO₃)₄ crystals were characterized. The visible luminescence spectra of (Pr,Y)Al₃(BO₃)₄ and PrAl₃(BO₃)₄ at 10 K and room temperature were measured.     

Optical properties and energy transfer among Nd in Nd:Ca2Al2SiO7 crystals for diode pumped lasers

The energy levels of neodymium in the Nd³⁺:Ca₂Al₂SiO₇ (CAS) laser material with gehlenite structure are reported. As the Nd³⁺:Ca₂Al₂SiO₇ compound presents a broad absorption around 806 nm, it is a good candidate for diode pumped laser. The ⁴F_3/2→⁴I_9/2 and ⁴F_3/2→⁴I11/2 emission have been recorded and the fluorescence branching ratios calculated from the Judd-Ofelt analysis are 0.41 and 0.47 respectively. The emission cross section at 1.06 μm (⁴F_3/2→⁴I11/2 transition) is 5 × 10^-20 cm². The decay profiles of the Nd³⁺ emission have been analyzed for several Nd³⁺ concentrations using the kinetic microparameters related to the cross relaxation ( and R₀≈6 Å) and the energy migration probabilities ( ). In the Nd:CAS laser material, the optimal concentration corresponding to the maximum of the fluorescence intensity is determined to be around 2.7 × 10²⁰ Nd³⁺ ions cm^-3. The Nd³⁺-Nd³⁺ interactions are not very strong in this material as the optical concentration value is two times higher than in the Nd:YAG laser material.