Luminescence and EPR studies of Mn-activated SrAl12O19 phosphor prepared by facile combustion approach

Manganese-activated strontium hexa-aluminate (SrAl₁₂O₁₉) phosphor has been prepared at low temperature (500 °C) and in a very short time (<5 min) by urea combustion route. Powder X-ray diffraction pattern showed the presence of hexagonal SrAl₁₂O₁₉ phase. Scanning electron microscopy (SEM) indicated the presence of several particles with sizes of 200 nm. The luminescence of Mn²⁺ activated SrAl₁₂O₁₉ exhibits a strong green emission peak around 515 nm from the synthesized phosphor particles under excitation (451 nm). The luminescence is assigned to a transition from the upper ⁴T₁→⁶A₁ ground state of Mn²⁺ ions. EPR investigations also indicated the presence of Mn²⁺ ions in the prepared material. From the observed EPR spectrum, the spin-Hamiltonian parameters have been evaluated. The magnitude of the hyperfine splitting (A) constant indicates that there exists a moderately covalent bonding between Mn²⁺ ions and the surrounding ligands. The variation of zero-field splitting parameter (D) with temperature is measured and discussed. The mechanism involved in the generation of a green emission has been explained in detail.     

Synthesis and optical properties of Er and Eu doped SrAl2O4 phosphor ceramic

We report, for the first time on luminescence from a Er³⁺ doped SrAl₂O₄ phosphor. Effects of Eu³⁺ doping were also studied. The influence of rare-earth doping in crystal structure and its optical properties were analysed by means of X-ray diffraction (XRD), Raman scattering, optical absorption, excitation and emission (PL) spectroscopy, thermally stimulated luminescence (TSL) and scanning electron microscope (SEM). Luminescence spectra and luminescence decay curves for Er³⁺ transitions in the near infrared region were recorded. The PL maximum for Eu doped SrAl₂O₄ is obtained at 620 nm and corresponds to the orange region of the spectrum. Diffraction patterns reveal a dominant phase, characteristic of the monoclinic SrAl₂O₄ compound and the presence of dopants has no effect on the basic crystal structure of SrAl₂O₄. The shapes of the glow curves are different for each dopant irradiated with either a ⁹⁰Sr-⁹⁰Y beta source, or UV light at 311 nm, and in detail the TL signals differ somewhat between Er and Eu dopants.     

Persistent luminescence dosimetric properties of UV-irradiated SrAl2O4:Eu, Dy phosphor

Current radiation dosimetry methods involve the release of trapped charge carriers in the form of electrons-holes pairs generated by irradiation exposure of the dosimetric materials. Thermal and optical stimulations of the irradiated material freed the trapped charges that eventually recombine with interband centers producing the emission of light. The integrated intensity of the emitted light is proportional to the radiation dose exposure. In this work, we present an UV radiation dosimetry technique based on the characteristic persistence luminescence (PLUM) 4f⁶5d¹→4f⁷ electronic transition of Eu²⁺ ions in SrAl₂O₄:Eu²⁺, Dy³⁺. The dose assessment is carried out by measuring the PLUM signal integrated during a certain time. The PLUM performance of SrAl₂O₄:Eu²⁺, Dy³⁺ phosphor exhibited a linear behavior for the first 50 s of UV irradiation. For higher UV time exposure the behavior is sublinear with no apparent saturation during a 10 min period. The PLUM dosimetry response was performed at 400 nm that corresponds to the main band component of the PLUM excitation spectrum in the 250-500 nm range. The main advantage of a dosimeter device based on the PLUM of SrAl₂O₄:Eu²⁺, Dy³⁺ is that neither thermal nor optical stimulation is required, avoiding the need of cumbersome electronic photo/thermal stimulation equipment. Due to the highly efficient 250-500 nm PLUM response of SrAl₂O₄:Eu²⁺, Dy³⁺, it could have potential application as UV radiation dosimeter in the UV range of grate human health concerns caused by UV solar radiation.     

Luminescence of BaAl2O4:Mn,Ce phosphor

Powder samples of barium aluminate doped with Mn²⁺ and Ce³⁺ were prepared by solid-state reaction method and their photoluminescence and thermoluminescence properties were studied. Substitution of Ca/Sr in place of Ba resulted in enhanced emission from Ce³⁺ ions without changing the spectral profile. Cerium efficiently sensitized the manganese luminescence in barium aluminate. Photoluminescence and thermo luminescence observations have indicated the presence of V_k³⁺ defects in undoped barium aluminate. However, Barium aluminate (either undoped or doped with manganese) did not exhibit long afterglow.     

Luminescence studies on the blue-green emitting Sr4Al14O25:Ce phosphor synthesized through solution combustion route

New blue-green emitting Sr₄Al₁₄O₂₅:Ce³⁺ phosphor is reported in this paper. The polycrystalline samples of phosphor were prepared by the conventional solution combustion method and checked for crystallization and phase by X-ray diffraction. Photoluminescence studies reveal the emission at 472 and 511 nm that correspond to the transition between lowest T_2g level of the 5d state to the ²F_5/2 and ²F_7/2 ground state levels of the Ce³⁺. The excitation at 275 nm corresponds to O²⁻→Ce⁴⁺ charge transfer processes to lowest 5d state of Ce ion (T_2g). Phosphorescence decay procedures reveal the existence of slow, medium, and fast component involved in the process. Varying the γ-dose (1-6 Gy), thermoluminescence (TL) measurements were made and glow curve maximum is obtained at 383 K. The phosphor seems to follow a first-order kinetics due to non-shifting T_m property. The T_m-T_stop method followed by the repeated initial rise method is applied to determine the distribution of activation energies and corresponding maximum positions. Chi-square minimization procedures provide the appropriate peak positions and other trapping parameters. From deconvolution results, the activation energies are found to be 0.84 and 1.06 eV, while the frequency factor is of the order of 10¹⁰ and 10¹¹ s⁻¹, respectively.     

Effect of temperature on the luminescence processes of SrAl2O4:Eu

The UV excited and persistent luminescence properties as well as thermoluminescence (TL) of Eu²⁺ doped strontium aluminates, SrAl₂O₄:Eu²⁺ were studied at different temperatures. Two luminescence bands peaking at 445 and 520 nm were observed at 20 K but only the latter at 295 K. Both Sr-sites in the lattice are thus occupied by Eu²⁺ but at room temperature efficient energy transfer occurs between the two sites. The UV excited and persistent luminescence spectra were similar at 295 K but the excitation spectra were different. Thus the luminescent centre is the same in both phenomena but excitation processes are different. Two TL peaks were observed between 50 and 250 °C in the glow curve. Multiple traps were, however, observed by preheating and initial rise methods. With longer delay times only the high temperature TL peak was observed. The persistent luminescence is mainly due to slow fading of the low temperature TL peak but the step-wise feeding process from high temperature traps is also probable.     

Photoluminescence and EPR studies of BaMgAl10O17:Eu phosphor with blue-emission synthesized by the solution combustion method

A blue phosphor, BaMgAl₁₀O₁₇:Eu²⁺, has been synthesized in the furnace at a temperature of 500 °C by solution combustion method. The formation of the as-prepared BaMgAl₁₀O₁₇:Eu²⁺ phosphor was confirmed by the powder X-ray diffraction technique. The EPR spectrum exhibited an intense resonance signal centered at g=4.63 at 150 mT along with a number of resonances in the vicinity of g>2.0 and g<2.0. The number of spins participating in resonance (N) and the susceptibility (c) for the resonance signal at g=4.63 have been calculated as a function of temperature. The excitation spectrum of BaMgAl₁₀O₁₇:Eu²⁺ phosphor showed a strong peak near 336 nm (4f⁷ (⁸S)→5d¹(t_2g) transition) with a staircase like structure in the region 376-400 nm owing to crystal field splitting of the Eu²⁺ d-orbital. The 336 nm excitation produced a broad blue emission at 450 nm corresponding to 4f⁶5d→4f⁷ transition. PL studies reveal the two emission centers one at 450 nm and the other at 490 nm in this phosphor.     

NIR to visible upconversion in Er/Yb co-doped CaYAl3O7 phosphor obtained by solution combustion process

Using the combustion synthesis, CaYAl₃O₇:Er³⁺ phosphor powders co-doped with Yb³⁺ have been prepared at low temperatures (550 °C) in a few minutes. Formation of the compound was confirmed by X-ray powder diffraction. Near-infrared to visible upconversion fluorescence emission in the Er³⁺ doped CaYAl₃O₇ phosphor powder has been observed. The effect of co-doping with triply ionized ytterbium in the CaYAl₃O₇:Er³⁺ phosphor has been studied and the process involved is discussed.     

Broad yellow orange emission from SrAl2O4:Pr phosphor with blue excitation for application to white LEDs

Photoluminescence excitation to intermediate atomic levels of rare earth activator ion (praseodymium) situated intragap in alkaline earth aluminate (AEA) SrAl₂O₄ has been tailored. This lead to blue excitation (2.7 eV) of large band gap AEA possible. Photoluminescence (PL) emission in the visible region extends from 525 to 650 nm corresponding to transition from ³P₀ and ¹D₂ excited states to different ³H_J and ³F_J states of Pr³⁺, broadened by crystal field effect of SrAl₂O₄. Thus SrAl₂O₄:Pr³⁺ promise to be a good candidate for solid state lighting in conjunction with blue LED.     

Luminescence in trivalent rare earth activated Sr4Al2O7 phosphor

In this paper we report the combustion synthesis of trivalent rare-earth (RE³⁺ = Dy, Eu and Ce) activated Sr₄Al₂O₇ phosphor. The prepared phosphors were characterized by the X-ray powder diffraction (XRD) and photoluminescence (PL) techniques. Photoluminescence emission peaks of Sr₄Al₂O₇:Dy³⁺ phosphor at 474 nm and 578 nm in the blue and yellow region of the spectrum. The prepared Eu³⁺ doped phosphors were excited by 395 nm then we found that the characteristics emission of europium ions at 615 nm (⁵D₀?⁷F₂) and 592 nm (⁵D₀?⁷F₁). Photoluminescence (PL) peaks situated at wavelengths of 363 and 378 nm in the UV region under excitation at around 326 nm in the Sr₄Al₂O₇:Ce³⁺ phosphor.     

Luminescence properties of Ce and Tb co-activated ZnAl2O4 phosphor

In this study, a solution combustion method was used to prepare green emitting Ce³⁺–Tb³⁺ co-activated ZnAl₂O₄ phosphor. The samples were annealed at 700 °C in air or hydrogen atmosphere to improve their crystallinity and optical properties. X-ray diffraction study confirmed that both as-prepared and post-preparation annealed samples crystallized in the well known cubic spinel structure of ZnAl₂O₄. An agglomeration of irregular platelet-like particles whose surfaces were encrusted with smaller spheroidal particles was confirmed by scanning electron microscopy (SEM). The fluorescence data collected from the annealed samples with different concentrations of Ce³⁺ and Tb³⁺ show the enhanced green emission at 543 nm associated with ⁵D₄→⁷F₅ transitions of Tb³⁺. The enhancement was attributed to energy transfer from Ce³⁺ to Tb³⁺. Possible mechanism of energy transfer via a down conversion process is discussed. Furthermore, cathodoluminescence (CL) intensity degradation of this phosphor was also investigated and the degradation data suggest that the material was chemically stable and the CL intensity was also stable after 10 h of irradiation by a beam of high energy electrons.     

PL and CL degradation and characteristics of SrAl2O4: Eu,Dy phosphors

Strontium aluminate phosphors are ideal for luminescent infrastructure materials. Their brightness and persistent glow time are much higher than previously used sulphide phosphors. Strontium aluminates prepared by the sol–gel and combustion methods are compared with commercially available strontium aluminate. High luminescent efficient SrAl₂O₄:Eu²⁺,Dy³⁺ pulsed laser deposited (PLD) thin films were also produced using the commercially available powder. Photoluminescence (PL) degradation studies showed that the phosphor intensity decreased about 20% over a period of 2 weeks under ultraviolet (UV) irradiation. Auger electron spectroscopy (AES) and X-ray photoelectron spectroscopy (XPS) showed that cathodoluminescence (CL) degradation is due to the formation of SrO due to electron stimulated surface reactions. The light output mechanism of the phosphor is also discussed in more detail.     

PrS0→Cr energy transfer and ESR investigation in Pr and Cr activated SrAl12O19 quantum cutting phosphor

With the help of the Dexter's theory, the energy transfer mechanism from Pr³⁺¹S₀ to Cr³⁺ is investigated theoretically in SrAl₁₂O₁₉:Pr³⁺, Cr³⁺ quantum cutting phosphors. The electron spin resonance (ESR) spectra of Pr³⁺ and Cr³⁺-doped SrAl₁₂O₁₉ with magnetoplumbite structure have been studied. The Cr³⁺ ion is found to enter the Al4(4f) site, which is very close to the Sr(2d) site replaced by the Pr³⁺ ions in the host. The theoretical results indicate that the efficient Pr³⁺¹S₀→Cr³⁺ energy transfer can only take place in the intermediate mirror planes, in which for the nearest and next-nearest Pr³⁺-Cr³⁺ pairs, both dipole-dipole and dipole-quadrupole interactions can play their parts in the transfer. Finally, an overview is given about the research on the energy transfer from Pr³⁺¹S₀ to codopants in their co-doped materials.     

Luminescence in LaCaAl3O7 prepared by combustion synthesis

LaCaAl₃O₇ phosphors activated by several ns² impurities like Pb²⁺ and Bi³⁺, and rare-earth dopants were prepared by combustion synthesis. X-ray diffraction (XRD) results confirmed the formation of single-phase compounds. Variety of activators exhibited interesting photoluminescence in LaCaAl₃O₇ host. Combustion synthesis furnishes a quick method for preparing these phosphors. It is suggested that LaCaAl₃O₇-based materials can be developed as low-cost phosphors.     

Combustion synthesized MgAl2O4:Cr phosphors—An EPR and optical study

Magnesium aluminate (MgAl₂O₄) doped with trivalent chromium (Cr³⁺) was synthesized by the combustion method. The prepared sample was characterized by X-ray powder diffraction, Brunauer-Emmet-Teller (BET) adsorption isotherms and diffuse-reflectance UV-vis spectroscopy techniques. Electron paramagnetic resonance (EPR) and photoluminescence (PL) studies have been performed at room temperature and at 110 K. The EPR spectrum exhibit resonance signals at g=5.37, 4.53, 3.82, 2.26 and 1.96 characteristic of Cr³⁺ ions. The luminescence of Cr³⁺-activated MgAl₂O₄ exhibits a red emission peak around 686 nm from the synthesized phosphor particles upon 551 nm excitation. The luminescence is assigned to a transition from the upper ²E_g→⁴A_2g ground state of Cr³⁺ ions. By correlating EPR and optical data the crystal field splitting parameter (D_q), Racah inter-electronic repulsion parameter (B) and the bonding parameters have been evaluated and discussed. The bonding parameters suggests that the ionic nature of Cr³⁺ ions with the ligands and the Cr³⁺ ions are in distorted octrahedral environment.     

Surface characterization and luminescent properties of SrAl2O4:Eu,Dy nano thin films

SrAl₂O₄:Eu²⁺, Dy³⁺ thin films were grown on Si (1 0 0) substrates in different atmospheres using the pulsed laser deposition (PLD) technique. The effects of vacuum, oxygen (O₂) and argon (Ar) deposition atmospheres on the structural, morphological and photoluminescence (PL) properties of the films were investigated. The films were ablated using a 248 nm KrF excimer laser. Improved PL intensities were obtained from the unannealed films prepared in Ar and O₂ atmospheres compared to those prepared in vacuum. A stable green emission peak at 520 nm, attributed to 4f⁶5d¹→4f⁷ Eu²⁺ transitions was obtained. After annealing the films prepared in vacuum at 800 °C for 2 h, the intensity of the green emission (520 nm) of the thin film increased considerably. The amorphous thin film was crystalline after the annealing process. The diffusion of adventitious C into the nanostructured layers deposited in the Ar and O₂ atmospheres was most probably responsible for the quenching of the PL intensity after annealing.     

Mn, Cr-co-doped MgAl2O4 phosphors for white LEDs

The Mn-, Cr-doped and Mn, Cr-co-doped MgAl₂O₄ powders have been synthesized via a gel-solid reaction method. Energy transfer from Mn²⁺ to Cr³⁺ has been observed for the first time in the co-doped MgAl₂O₄ phosphors. When excited with blue light with a wavelength of 450 nm at room temperature, both green emission from Mn²⁺ around 520 nm and red emission from Cr³⁺ around 675and 693 nm were generated. Moreover, the color of the emission can be modified by controlling the doping concentrations of Mn²⁺ and Cr³⁺. Therefore, MgAl₂O₄: Mn²⁺, Cr³⁺ could be used as a single-phased phosphor for white LED with a blue LED chip. The energy transfer in terms of Mn²⁺ to Cr³⁺ is determined by means of radiation and reabsorption.     

EPR and luminescence properties of LiGa5O8:Mn green emitting phosphor

Green emitting LiGa₅O₈:Mn powder phosphor has been prepared in a short time by solution combustion method. Powder X-ray diffraction pattern indicated a dominant phase of LiGa₅O₈ with another secondary LiGaO₂ phase. Morphology aspects were studied by using field emission scanning electron microscopy. Upon UV light excitation (296 nm), the phosphor exhibits a strong green luminescence (510 nm), which corresponds to the ⁴T₁→⁶A₁ transition of Mn²⁺ ions in an environment close to tetrahedral symmetry. EPR spectrum exhibits resonance signals characteristic of Mn²⁺ ions. It is observed that the spin-Hamiltonian parameters g and A do not vary with temperature. The magnitude of the hyperfine splitting constant (A) in the present study indicates that there exists a moderately covalent bonding between Mn²⁺ ions and the surrounding ligands. The zero-field splitting parameter (D), spin concentration (N) and paramagnetic susceptibility (χ) have also been evaluated.     

Synthesis of nano-size BaMgAl10O17:Eu blue phosphor by a rapid exothermic reaction

Ultrafine particles of BaMgAl₁₀O₁₇:Eu²⁺ (BAM) phosphor were synthesized by a solid-state combustion reaction in a powder bed of 0.9BaCO₃+MgO+5Al₂O₃+0.05Eu₂O₃+k(KClO₃+1.5C) composition. A large exothermic reaction of the mixture (KClO₃+1.5C) leads to a self-sustaining combustion mode. Under optimized combustion conditions, the product consisted of BAM powder and KCl was obtained. BAM ultrafine particles resulting from the combustion process were easily obtained by simply washing the salt by-product with water. Combustion-processed BAM phosphor shows a homogeneous grain size of 100-500 nm, good dispersity, regular morphology, and improved luminescence properties.     

Phosphorescent and thermoluminescent properties of SrAl2O4:Eu,Dy phosphors prepared by solid state reaction method

Long persistent SrAl₂O₄:Eu²⁺ phosphors co-doped with Dy³⁺ were prepared by the solid state reaction method. The main diffraction peaks of the monoclinic structure of SrAl₂O₄ were observed in all the samples. The broad band emission spectra at 497 nm for SrAl₂O₄:Eu²⁺, Dy³⁺ were observed and the emission is attributed to the 4f⁶5d¹ to 4f⁷ transition of Eu²⁺ ions. The samples annealed at 1100–1200 °C showed similar broad TL glow curves centered at 120 °C. The similar TL glow curves suggest that the traps responsible for them are similar. The long afterglow displayed by the phosphors annealed at different temperatures, may be attributed to the Dy³⁺ ions acting as the hole trap levels, which play an important role in prolonging the duration of luminescence.