Enhanced photoluminescence of CaTiO3:Pr phosphor films deposited on SiO2 buffered Si substrates

CaTiO₃:Pr³⁺ films have been prepared by pulsed-laser deposition method on SiO₂-buffered Si substrates, and their microstructure and photoluminescence properties have been compared with those of the films deposited directly on bare Si substrates. The SiO₂ buffer layers were prepared using thermal oxidization and HF-etching. Photoluminescence intensities of CaTiO₃:Pr³⁺ films on the SiO₂-buffered Si substrates are significantly higher (up to 800%) than those of the films on bare Si substrates, which is attributed to the low refractive index and low light absorption of the SiO₂ buffer layer. This study reveals that the presence of the buffer layer is effective in improving the red emission brightness of CaTiO₃:Pr³⁺ films without sacrificing the surface roughness.     

Emission properties of (SrTiO3-TiO2):Pr eutectic with self-organized fractal microstructure

An investigation of spectroscopic properties of (SrTiO₃-TiO₂):Pr³⁺ eutectic and, for comparison, of bulk SrTiO₃:Pr³⁺ and TiO₂:Pr³⁺crystals is presented. Luminescence spectra have been measured under both 450 nm and 350 nm excitation wavelength. For UV excitation they are characterized by a dominant red luminescence corresponding to transition from the ¹D₂ level of Pr³⁺ ions. The mechanism responsible for quenching of blue (from ³P₀ state) and intensification of red luminescence is proposed to be thermally-induced radiationless relaxation involving a low-lying Pr³⁺-Ti⁴⁺ intervalence charge transfer state. Measured decay constants of ¹D₂ excited state of Pr³⁺ are compared with values obtained for other praseodymium doped titanate hosts.     

Synthesis and blue to near-infrared quantum cutting of Pr/Yb co-doped Li2TeO4 phosphors

Near-infrared (NIR) quantum cutting luminescent materials Li₂TeO₄ doped with Pr³⁺ and Yb³⁺ were synthesized by solid-state reaction method. The dependence of Yb³⁺ doping concentration on the visible- and NIR-emissions, decay lifetime, and quantum efficiencies of the phosphors are investigated. Quantum cutting down-conversion involving 647 nm red emission and 960-1050 nm broadband near-infrared emission for each 487 nm blue photon absorbed is realized successfully in the resulting phosphors, of which the process of near-infrared quantum cutting could be expressed as ³P₀(Pr³⁺) → ²F_5/2(Yb³⁺) + ²F_5/2(Yb³⁺). The maximum quantum cutting efficiency approaches up to 166.4% in Li₂TeO₄: 0.3 mol%Pr³⁺, 1.8 mol%Yb³⁺ sample corresponding to the 66.4% value of energy transfer efficiency.     

The influence of the Pr 4f5d configuration on the S0 emission efficiency and lifetime in LaPO4

The photoluminescence and excitation spectra of Pr³⁺ activated LaPO₄ has been investigated in the 1.6-300 K temperature region. At room temperature, the luminescence of LaPO₄:Pr³⁺ is composed of the interconfigurational 4f¹5d¹ → 4f² emission transitions. However, in the 1.6-60 K temperature range, the emission spectrum also consists of the intraconfigurational emission transitions that emanate from the ¹S₀ state. A radiative lifetime of 145 ns is measured for the Pr³⁺¹S₀ → ¹I₆ emission transition in LaPO₄. This is one of the shortest radiative lifetime observed for this transition in a solid. The energy position of the Pr³⁺¹S₀ state in LaPO₄ is established by high-resolution emission spectrum at 46 375 ± 5 cm⁻¹. A detailed analysis of the thermal quenching of the ¹S₀ lifetime and emission intensity is presented. It is proposed that the lowest energy state of the relaxed 4f¹5d¹ configuration is situated energetically below that of the ¹S₀ state.     

Enhanced G4 emission in NaLaF4: Pr, Yb and charge transfer in NaLaF4: Ce, Yb studied by fourier transform luminescence spectroscopy

A high resolution luminescence study of NaLaF₄: 1%Pr³⁺, 5%Yb³⁺ and NaLaF₄: 1%Ce³⁺, 5%Yb³⁺ in the UV to NIR spectral range using a InGaAs detector and a fourier transform interferometer is reported. Although the Pr³⁺(³P₀ → ¹G₄), Yb³⁺(²F_7/2 → ²F_5/2) energy transfer step takes place, significant Pr³⁺¹G₄ emission around 993, 1330 and 1850 nm is observed. No experimental proof for the second energy transfer step in the down-conversion process between Pr³⁺ and Yb³⁺ can be given. In the case of NaLaF₄: Ce³⁺, Yb³⁺ it is concluded that the observed Yb³⁺ emission upon Ce³⁺ 5d excitation is the result of a charge transfer process instead of down-conversion.     

Luminescence characteristic of YVO4:Eu thin film phosphors by Li doping

YVO₄:Eu³⁺ and Li-doped YVO₄:Eu³⁺ thin film phosphors have been deposited on Al₂O₃ (0001) substrate using a pulsed laser deposition technique. The Li⁺ ions concentration was varied from 0 to 3 wt.% and Li⁺ doping influenced crystallinity and surface morphology of YVO₄:Eu³⁺ films.. As Li⁺ content increases from 0 wt.% to 2 wt.%, not only crystallinity was improved, but also the shape of grains was rounded. However, Li⁺ content, increases further to 3 wt.% the shape of grains was changed to elliptical. The emitted radiation was dominated by a red emission peak at 619 nm radiated from the ⁵D₀-⁷F₂ transition of Eu³⁺ ions. In particular, the incorporation of Li⁺ ions into YVO₄ lattice could induce an increase of photoluminescence. The enhanced luminescence results not only from the improved crystallinity but also from the enhanced surface roughness. The luminescent intensity and surface roughness exhibited similar behavior as a function of Li⁺ ions concentration.     

White light generation in Al2O3:Ce:Tb:Mn films deposited by ultrasonic spray pyrolysis

Aluminium oxide (Al₂O₃) films doped with CeCl₃, TbCl₃ and MnCl₂ were deposited at 300 °C with the ultrasonic spray pyrolysis technique. The films were analysed using the X-ray diffraction technique and they exhibited a very broad band without any indication of crystallinity, typical of amorphous materials. Sensitization of Tb³⁺ and Mn²⁺ ions by Ce³⁺ ions gives rise to blue, green and red simultaneous emission when the film activated by such ions is excited with UV radiation. The overall efficiency of such energy transfer results to be about 85% upon excitation at 312 nm. Energy transfer from Ce³⁺ to Tb³⁺ ions through an electric dipole-quadrupole interaction mechanism appears to be more probable than the electric dipole-dipole one. A strong white light emission for the Al₂O₃:Ce³⁺(1.3 at.%):Tb³⁺(0.2 at.%):Mn²⁺(0.3 at.%) film under UV excitation is observed. The high efficiency of energy transfer from Ce³⁺ to Tb³⁺ and Mn²⁺ ions, resulting in cold white light emission (x = 0.30 and y = 0.32 chromaticity coordinates) makes the Ce³⁺, Tb³⁺ and Mn²⁺ triply doped Al₂O₃ film an interesting material for the design of efficient UV pumped phosphors for white light generation.     

Enhanced red emission in ZnB2O4:Eu by charge compensation

Eu³⁺ doped ZnB₂O₄ without or with different charge compensation (CC) approaches (co-doping Li⁺, Na⁺, K, decreasing the content of Zn²⁺) were prepared by solid state reactions. The phosphors can strongly absorb 393 nm ultraviolet (UV) light which is coupled well with the emission of currently used InGaN-based near UV light emitting diodes (LEDs) and emit red light with a good color purity. The luminescent intensity of phosphors can be remarkably enhanced with any of CC methods. However, the shape and position of excitation and emission spectra keep unchanged. The introduction of Li⁺ can enhance the red emission intensity of Eu³⁺ by ∼4 times with the optimal effect. Red emission of Eu³⁺ can also be enhanced with the other three CC approaches but the effects are not as good as Li⁺ because the volume unbalance in Li⁺ compensation approach is the smallest while net positive charge was offset. The results of this work suggest that volume compensation and equilibrium of mole number should also be taken into account when a CC approaches is selected.     

Fast d-f emission in Ce, Pr and Nd activated RbCl

In the search for new scintillator materials, Ce³⁺ doped chlorides are a promising class of materials, combining a high efficiency and fast response time. Even shorter response times may be achieved by replacing Ce³⁺ by Pr³⁺ or Nd³⁺ as the lifetime of the d-f emission is substantially shorter for these ions. Here we report on the luminescence properties of Ce³⁺, Pr³⁺ and Nd³⁺ in RbCl and investigate the potential as a scintillator material. Under UV excitation Ce³⁺ shows d-f emission between 325 and 425 nm. The emission originates from multiple (differently charge compensated) Ce³⁺ sites. The luminescence lifetime varies with wavelength and is ∼40 ns for the longer wavelength emission. For RbCl:Pr³⁺ three d-f emission band are observed between 250 and 350 nm which can be assigned to transitions from the lowest energy fd state to different ³H_J (J = 4-6) states within the 4f² configuration of Pr³⁺. The decay time is ∼17 ns. For the Nd³⁺ activated sample a weak emission band around 220 nm is observed only at 8 K which may be due to d-f emission. The very short lifetime (4 ns) is faster than the radiative lifetime, indicating that the d-f emission is quenched by relaxation to lower lying 4f³ states or by the process of photoionization. Under VUV excitation at wavelengths below 175 nm (the bandgap of RbCl) the d-f emission is very weak for Ce³⁺, Pr³⁺ and Nd³⁺ doped RbCl and the emission spectra are dominated by defect related emission. This indicates that energy transfer from the host lattice to the fd states is inefficient which prevents application as a scintillator material.     

Efficiency enhancement by aluminum addition to CaTiO3:Pr phosphor thin films

The mechanism of enhancement of the red emission efficiency from CaTiO₃:Pr³⁺ thin film by Al addition has been investigated. Al-ions have been attracting interest as a sensitizer to improve the luminescent efficiency of phosphors. Also, influence of Al-doping on the crystallization, surface morphology and luminescent properties of CaTiO₃:Pr³⁺ thin films have been discussed. CaTiO₃:Pr³⁺ and Al-doped CaTiO₃:Pr³⁺ films were grown using pulsed laser deposition technique on Al₂O₃ (0001) substrates under different substrate temperatures and oxygen pressures. The crystalline phase and surface morphology of the films were very dependent on the oxygen pressure and substrate temperature and they affected the luminescent brightness of the films. The crystalline structure and microstructure of these films have been characterized by X-ray diffraction and electron microscopy and their luminescent properties have been evaluated at room temperature using a luminescence spectrometer and excitation by a broadband incoherent ultraviolet light source with a dominant excitation wavelength of 325 nm. In particular, the incorporation of Al³⁺ ions into CaTiO₃ lattice could induce a remarkable increase of photoluminescence. The enhancement of luminescence for Al-doped films may result not only from the improved crystallinity but also from the reduced internal reflections caused by rougher surfaces. Also, the luminescent intensity and surface roughness of the films exhibited similar behavior as a function of oxygen pressure.     

High pressure and time resolved luminescence spectra of Gd3Ga5O12:Pr crystal

Luminescence spectra and time resolved luminescence spectra of GGG crystal doped with Pr³⁺ were measured at high hydrostatic pressure from ambient to 220 kbar. Effect of pressure results in the red shift of all luminescence lines related to Pr³⁺ ion emission equals from −0.32 to −1.02 cm⁻¹/kbar and in the diminishing of the luminescence lifetimes. The luminescence decay related to emission from ³P₀ state was single-exponential and diminished with pressure from 23 μs at ambient pressure to 6.5 μs at 165 kbar. Luminescence decay related to transition form ¹D₂ state was two-exponential with longer decay equal to 162 μs at ambient pressure and 120 μs at 165 kbar. We discussed effect of pressure on the ¹D₂ → ³H₄ luminescence and emission from ³P₀ state in the context of non-radiative processes that depopulate the ³P₀ and populate the ¹D₂ state, considering mainly multiphonon relaxation processes and depopulation via the praseodymium trapped exciton state.     

Luminescence properties of Eu ions doped in Y2−xGdxO3 thin films grown by pulsed laser deposition method

Luminescence properties of Y_2−xGd_xO₃:Eu³⁺ (x = 0 to 2.0) thin films are investigated by site-selective laser excitation spectroscopy. The films were grown by pulsed laser deposition method on SiO₂ (100) substrates. Cubic phase Y₂O₃ and Gd₂O₃ and monoclinic phase Gd₂O₃ are identified in the excitation spectrum of the ⁷F₀ → ⁵D₀ transition of Eu³⁺. The emission spectra of the ⁵D₀ → ⁷F_J (J = 1 and 2) transition from individual Eu³⁺ centers were obtained by tuning the laser to resonance with each excitation line. The excitation line at around 580.60 nm corresponds to the line from Eu³⁺ with C₂ site symmetry of cubic phase. New lines at 578.65 and 582.02 nm for the C_S sites of Gd₂O₃ with monoclinic phase are observed by the incorporation of Gd in Y₂O₃ lattice. Energy transfer occurs between Eu³⁺ ions at the C_S sites and from Eu³⁺ ions at the C_S sites to those at the C₂ site in Y_2−xGd_xO₃.     

A red-emitting heavy doped phosphor Li6Y(BO3)3:Eu for white light-emitting diodes

A series of Eu³⁺ activated Li₆Y_1−xEu_x(BO₃)₃ (0.05 ? x ? 1) phosphors were synthesized by solid-state reaction method. The structures and photoluminescent properties of the phosphors were investigated at room temperature. The results of XRD patterns indicate that these phosphors are isotypic to the monoclinic Li₆Gd(BO₃)₃. The excitation spectra indicate that these phosphors can be effectively excited by near UV (370-410 nm) light. The red emission from transition ⁵D₀→⁷F₂ is dominant. The emission spectra exhibit strong red performance (CIE chromaticity coordinates: x = 0.65, y = 0.35), which is due to the ⁵D₀−⁷F_J transitions of Eu³⁺ ions. The relationship between the structure and the photoluminescent properties of the phosphors was studied. The concentration quenching occurs at x ≈ 0.85 under near UV excitation. Li₆Y(BO₃)₃:Eu³⁺ has potential application as a phosphor for white light-emitting diodes.     

Significant reduction of upconversion emission in CaTiO3: Yb, Er inverse opals

Inverse opal photonic crystals of Yb³⁺, Er³⁺ co-doped CaTiO₃ (CaTiO₃: Yb, Er) were prepared using self-assembled polystyrene templates combined with the infiltration of sol-gel precursor. The influence of the photonic band gap on upconversion emission of Er³⁺ has been investigated in the CaTiO₃: Yb, Er inverse opals. Significant reduction of the upconversion emission was detected if the photonic band-gap overlaps with the Er³⁺ ions emission band.     

Concentration effects on Pr luminescence in LaAlO3 crystals

Concentration dependant emission spectra and fluorescence dynamic profiles have been investigated in Pr_xLa_1−xAlO₃ single crystals in order to better understand processes responsible for concentration quenching of the praseodymium ³P₀ and ¹D₂ emissions. The cross-relaxation transfer rates were experimentally determined as a function of Pr³⁺ concentration. Decays were modeled and nearest-neighbor trapping rates were calculated.     

Blue-violet phosphate phosphor thin films for EL

Photoluminescence (PL) and electroluminescence (EL) in blue-violet emission were observed in newly developed phosphate phosphor thin films such as Ba₃(PO₄)₂:Eu and Ba₃(PO₄)₂:Ti. These phosphate phosphor thin films were first deposited on thick BaTiO₃ ceramic sheets by r.f. magnetron sputtering using powder targets and then post-annealed in various atmospheres. Blue-violet PL and EL emissions were obtained in Ba₃(PO₄)₂:Eu and Ba₃(PO₄)₂:Ti phosphor thin films that were deposited in an Ar + H₂ (10%) gas atmosphere and then post-annealed above about 900 °C in an Ar + H₂ (10%) gas atmosphere. In particular, the EL observed in Ba₃(PO₄)₂:Eu thin films exhibited two peaks, a red emission peaking at about 615 nm and a blue-violet emission peaking at about 420 nm. A luminance of 2.0 cd/m² in blue-violet emission was obtained in a thin-film EL device using a two step post-annealed Ba₃(PO₄)₂:Eu thin-film emitting layer: step 1, post-annealing at 1000 °C in air for 1 h, and step 2, post-annealing at 1000 °C in an Ar + H₂ atmosphere.     

Factors for determining photoluminescence properties of YBO3:Ce phosphor prepared by hydrothermal method

YBO₃:Ce³⁺ blue-emitting phosphors were prepared from boric acid and nitrates of yttrium and cerium(III) by hydrothermal method. An excess amount of boric acid, prolonged aging, high temperature, and a high pH value promote the formation of crystalline YBO₃. The higher crystallinity results in the higher photoluminescence (PL) intensity corresponding to the 5d-4f transition of Ce³⁺ under the irradiation of near-UV light. The PL intensity also depends on the pH value of precursor suspension and the nominal Ce³⁺ concentration, where the sample prepared at pH = 8 and Ce/(Y + Ce) = 0.25-0.5 at% shows the maximum PL intensity. In addition, the hydrothermally prepared sample shows the characteristic photobleaching behavior under the continuous irradiation of near-UV light. These results suggest that the crystallinity of the host YBO₃ crystal and the homogeneity of substituted Ce³⁺ ions play significant roles in the PL properties.     

The effect of In ion on the optical characteristics of Er in Er/Yb:LiNbO3 crystal

The effect of In³⁺ ion on the optical characteristics of Er³⁺ ion in Er/Yb:LiNbO₃ crystal under 980 nm excitation has been investigated. The Er and Yb contents in the crystals were measured by an inductively coupled plasma atomic emission spectrometer (ICP-AES). A significant enhancement of 1.54 μm emission was observed for Er/Yb:LiNbO₃ crystal doped with 1 mol% In₂O₃. The studies on the UV-vis absorption and the OH⁻ absorption spectra indicate that the threshold concentration of In³⁺ ion decreases with the Er/Yb doping in Er/Yb/In:LiNbO₃ crystal. The 1 mol% In₂O₃ doping results in the reduction of absorption cross section in the UV-vis region, meaning the formation of Er³⁺ cluster sites. The enhancement of 1.54 μm emission is attributed to the larger probabilities of the cross relaxation processes ⁴S_3/2 + ⁴I_15/2 → ⁴I_9/2 + ⁴I_13/2 (Er), ⁴S_3/2 + ⁴I_15/2 → ⁴I_13/2 + ⁴I_9/2 (Er) and ⁴I_9/2 + ⁴I_15/2 → ⁴I_13/2 + ⁴I_13/2 (Er) induced by Er³⁺ cluster sites.     

Preparation and upconversion property of TeO2:Er/Yb nanoparticles

Different crystal structure of TeO₂ nanoparticles were used as the host materials to prepare the Er³⁺/Yb³⁺ ions co-doped upconversion luminescent materials. The TeO₂ nanoparticles mainly kept the original morphology and phase after having been co-doped the Er³⁺/Yb³⁺ ions. All the as-prepared TeO₂:Er³⁺/Yb³⁺ nanoparticles showed the green emissions (525 nm, 545 nm) and red emission (667 nm) under 980 nm excitation. The green emissions at 525 nm, 545 nm and red emission at 667 nm were attributed to the ²H_11/2 → ⁴I_15/2, ⁴S_3/2 → ⁴I_15/2 and ⁴F_9/2 → ⁴I_15/2 transitions of the Er³⁺ ions, respectively. For the α-TeO₂:Er³⁺/Yb³⁺ (3/10 mol%) nanoparticles, three-photon process involved in the green (²H_11/2 → ⁴I_15/2) emission, while two-photon process involved in the green (⁴S_3/2→⁴I_15/2) and red (⁴F_9/2 → ⁴I_15/2) emissions. For the β-TeO₂:Er³⁺/Yb³⁺ (3/10 mol%) nanoparticles, two-photon process involved in the green (²H_11/2 → ⁴I_15/2), green (⁴S_3/2 → ⁴I_15/2) and red (⁴F_9/2 → ⁴I_15/2) emissions. It suggested that the crystal structure of TeO₂ nanoparticles had an effect on transition processes of the Er³⁺/Yb³⁺ ions. The emission intensities of the α-TeO₂:Er³⁺/Yb³⁺ (3/10 mol%) nanoparticles and β-TeO₂:Er³⁺/Yb³⁺ (3/10 mol%) nanoparticles were much stronger than those of the (α + β)-TeO₂:Er³⁺/Yb³⁺ (3/10 mol%) nanoparticles.     

Photoluminescence properties of β-Ga2O3:Tb nanofibers prepared by electrospinning

One-dimensional Tb³⁺-doped β-Ga₂O₃ nanofibers were prepared by a simple and cost-effective electrospinning process. Field emission scanning electron microscopy (FE-SEM), X-ray diffraction (XRD), Raman technique, and photoluminescence (PL) were used to characterize the electrospun nanofibers. FE-SEM results indicated that the diameters all of the nanofibers ranged from 100 to 300 nm, and the lengths of nanofibers reached up to several millimeters. The XRD and Raman results showed that the Ga₂O₃ phase belongs to the monoclinic phase. Under ultraviolet excitation, the β-Ga₂O₃:Tb³⁺ samples showed green emission with the strongest peak at 550 nm, corresponding to ⁵D₄ → ⁷F₅ transition of Tb³⁺ ions. The luminescence intensity had been further studied as a function of the doping concentration of Tb³⁺ in the β-Ga₂O₃ samples.