Photoluminescence in rare earth‐doped complex hexafluoride phosphors

In this study, using a simple combustion process and a wet chemical process, fluorides showing intense photoluminescence were prepared and developed as low‐cost phosphors. The prepared phosphors were characterized by photoluminescence (PL) techniques. PL emission spectra of the phosphor suggest the presence of Eu³⁺ as well as Eu²⁺ ions in LiMgBF₆:Eu and Li₂NaBF₆:Eu lattice sites. This article summarizes the fundamentals and possible applications of optically useful inorganic fluoride with visible photoluminescence of doped Eu³⁺ and Eu²⁺ ions. Our results on LiMgBF₆:Ce and Li₂NaBF₆:Ce are also reported. Copyright © 2011 John Wiley & Sons, Ltd.     

Structural and luminescent studies of erbium‐doped CaZrO3 green‐emitting nanophosphors

Erbium (Er) (0.5, 1.0 and 1.5 wt%)‐doped CaZrO₃ nanophosphors were synthesized by the sol–gel method using poly(vinyl alcohol) as the chelating agent. Their structural and photoluminescence properties were studied using X‐ray diffraction (XRD), field emission scanning electron microscopy–energy dispersive spectroscopy (FESEM‐EDS), transmission electron microscopy (TEM), photoluminescence and Fourier transform infrared spectroscopy (FTIR). The XRD patterns of the samples confirm that nanoscale crystallite sizes. Agglomeration of the samples was observed using field emission scanning electron microscopy images. Energy dispersive spectroscopy measurements confirmed the existence of Ca, Zr, O and Er in the samples. Average particle sizes for the samples were calculated from transmission electron microscopy images. FTIR spectra clearly show characteristic absorption bands related to the metal oxides, as well as some other organic molecules. The photoluminescence spectra show bands in the green region. The Commission International de l'Eclairage coordinates were calculated and found to be in green region.     

Infrared and visible emissions of rare‐earth‐doped CeO2 phosphor

This paper reports the synthesis and characterization of Er³⁺‐doped CeO₂ phosphor with variable concentrations of erbium. The sample was synthesized using a solid‐state reaction method, which is useful for the large‐scale production of phosphors and is also eco‐friendly. The prepared sample was characterized using an X‐ray diffraction (XRD) technique. The XRD pattern confirmed that sample has the pure cubic fluorite crystal structure of CeO₂. The crystallite size of the prepared phosphor was determined by Scherer's formula and the crystallite size giving an intense XRD peak is 40.06 nm. The surface morphology of the phosphor was determined by field emission gun scanning electron microscopy (FEGSEM). From the FEGSEM image, good surface morphology with some agglomerates was found. The functional group in the prepared sample was analysed by Fourier transform infrared (FTIR) spectroscopy. All samples prepared with variable concentrations of Er³⁺ (0.1–2 mol%) were studied by photoluminescence analysis and it was found that the excitation spectra of the prepared phosphor shows broad excitation centred at 251 nm. Emission spectra at different concentrations of Er³⁺ show strong peaks at 413 and 470 nm and a weaker peak at 594 nm. The dominant peaks at 413 and 470 nm are caused by the allowed electronic transition ⁴S_3/2 → ⁴I_15/2 and the weaker transition at 594 nm is due to the transition ⁴ F_9/2 → ⁴I_15/2. Spectrophotometric determinations of peaks were evaluated using the Commission Internationale de I'Eclairage (CIE) technique. The emission spectra were also observed using an infrared (IR) laser 980 nm source, and three distinct peaks were found in the IR region at 848, 870 and 980 nm. The prepared phosphor has utility for application in display devices. Copyright © 2015 John Wiley & Sons, Ltd.     

Structure and photoluminescent properties of green‐emitting terbium‐doped GdV1−xPxO4 phosphor prepared by solution combustion method

Terbium‐doped gadolinium orthovanadate (GdVO₄:Tb³⁺), orthophosphate monohydrate (GdPO₄·H₂O:Tb³⁺) and orthovanadate–phosphate (GdV,PO₄:Tb³⁺) powder phosphors were synthesized using a solution combustion method. X‐Ray diffraction analysis confirmed the formation of crystalline GdVO₄, GdPO₄·H₂O and GdV,PO₄. Scanning electron microscopy images showed that the powder was composed of an agglomeration of particles of different shapes, ranging from spherical to oval to wire‐like structures. The chemical elements present were confirmed by energy dispersive spectroscopy, and the stretching mode frequencies were determined by Fourier transform infrared spectroscopy. UV–visible spectroscopy spectra showed a strong absorption band with a maximum at 200 nm assigned to the absorption of VO₄^3? and minor excitation bands assigned to f → f transitions of Tb³⁺. Four characteristic emission peaks were observed at 491, 546, 588 and 623 nm, and are attributed to ⁵D₄ → ⁷F_j (j = 6, 5, 4 and 3). The photoluminescent prominent green emission peak (⁵D₄ → ⁷F₅) was centred at 546 nm. The structure and possible mechanism of light emission from GdV_1?xP_xO₄:% Tb³⁺ are discussed. Copyright © 2016 John Wiley & Sons, Ltd.     

Structural characterization of Er3+,Yb3+‐doped Gd2O3 phosphor,synthesized using the solid‐state reaction method,and its luminescence behavior

We report the synthesis and structural characterization of Er³⁺,Yb³⁺‐doped Gd₂O₃ phosphor. The sample was prepared using the conventional solid‐state reaction method, which is the most suitable method for large‐scale production. The prepared phosphor sample was characterized using X‐ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), Fourier transform infrared spectroscopy (FTIR), thermoluminescence (TL), photoluminescence (PL) and CIE techniques. For PL studies, the excitation and emission spectra of Gd₂O₃ phosphor doped with Er³⁺ and Yb³⁺ were recorded. The excitation spectrum was recorded at a wavelength of 551 nm and showed an intense peak at 276 nm. The emission spectrum was recorded at 276 nm excitation and showed peaks in all blue, green and red regions, which indicate that the prepared phosphor may act as a single host for white light‐emitting diode (WLED) applications, as verified by International de I'Eclairage (CIE) techniques. From the XRD data, the calculated average crystallite size of Er³⁺ and Yb³⁺‐doped Gd₂O₃ phosphor is ~ 38 nm. A TL study was carried out for the phosphor using UV irradiation. The TL glow curve was recorded for UV, beta and gamma irradiations, and the kinetic parameters were also calculated. In addition, the trap parameters of the prepared phosphor were also studied using computerized glow curve deconvolution (CGCD). Copyright © 2015 John Wiley & Sons, Ltd.     

Synthesis of the long‐persistence phosphor CaAl2O4:Eu2+, Dy3+, Nd3+ by combustion method and its luminescent properties

Calcium aluminate phosphor co‐doped Eu²⁺, Dy³⁺, Nd³⁺ is prepared by the combustion method. We study systemically the influences of the quantity of mixed Dy³⁺ ion, the quantity of flux H₃BO₃, the differences in dispersing methods between magnetic stirring and ultrasonic dispersing and the combustion temperature on the long‐persistence phosphor. The analytical results indicate that Dy³⁺ ion improves the properties of the phosphors CaAl₂O₄:Eu²⁺, Nd³⁺. The appropriate quantity of flux H₃BO₃ to reduce the forming temperature of the sample was determined. The monoclinic single phase of CaAl₂O₄ formed at 500°C and remained steady. The calcium aluminate co‐doped Eu²⁺, Dy³⁺, Nd³⁺ was synthesized by dispersal of the raw material using the ultrasonic method, and it had better optical properties. Copyright © 2009 John Wiley & Sons, Ltd.     

Structural and photoluminescence study of Mn2+‐activated CaYAl3O7 blue phosphors

The structural and photoluminescence properties of CaYAl₃O₇ phosphor material doped with varying concentration of Mn²⁺ have been studied. The phosphor material was synthesized by the combustion method at 500 °C and was characterized using X‐ray diffraction, Fourier transform infrared spectroscopy and photoluminescence spectroscopy (PL). X‐ray diffraction showed that the crystallites have average sizes in the range of ~58–70 nm. Corresponding Fourier transform infrared spectroscopy investigations confirm the phase formation and the presence of aluminate group (Al‐O bands) in CaYAl₃O₇:Mn²⁺ phosphor. Under the excitation at 356 nm wavelength, the PL spectra show the occurrence of two emission peaks obtained in the blue region at 389 nm and 412 nm, which is attributed to the 4 T1(G) → 6A1 transition of Mn²⁺ ion. Upon increasing Mn²⁺ concentration, the relative PL intensity shows an initial decrement followed by an increase displaying the effect of concentration quenching. Overall the results suggest the possibility of using this material in white lighting devices and plasma display panels. Copyright © 2013 John Wiley & Sons, Ltd.     

Photoluminescence in K3Ca2(SO4)3Cl‐doped Eu3+ phosphor

In this article we report Eu³⁺ luminescence in novel K₃Ca₂(SO₄)₃Cl phosphors prepared by wet chemical methods. The Eu³⁺ emission was observed at 594 nm and 615 nm, keeping the excitation wavelength constant at 396 nm nearer to light‐emitting diode excitation, Furthermore, phosphors were characterized by X‐ray diffraction for the confirmation of crystallinity. The variation of the photoluminescence intensity with impurity concentration has also been discussed. Thus, prominent emission in the red region makes prepared phosphors more applicable for white light‐emitting diodes. Copyright © 2013 John Wiley & Sons, Ltd.     

Luminescence study and dosimetry approach of Ce on an α‐Sr2P2O7 phosphor synthesized by a high‐temperature combustion method

We report synthesis of a cerium‐activated strontium pyrophosphate (Sr₂P₂O₇) phosphor using a high‐temperature combustion method. Samples were characterized by X‐ray diffraction (XRD), Fourier transform infrared spectroscopy (FT‐IR), photoluminescence (PL) and thermoluminescence (TL). The XRD pattern reveals that Sr₂P₂O₇ has an α‐phase with crystallization in the orthorhombic space group of Pnam. The IR spectrum of α‐Sr₂P₂O₇ displays characteristic bands at 746 and 1190 cm^‐1 corresponding to the absorption of (P₂O₇)^‐4. PL emission spectra exhibit a broad emission band around 376 nm in the near‐UV region due to the allowed 5d–4f transition of cerium and suggest its applications in a UV light‐emitting diode (LED) source. PL also reveals that the emission originates from 5d–4f transition of Ce³⁺ and intensity increases with doping concentration. TL measurements made after X‐ray irradiation, manifest a single intense glow peak at around 192°C, which suggests that this is an outstanding candidate for dosimetry applications. The kinetic parameters, activation energy and frequency factor of the glow curve were calculated using different analysis methods. Copyright © 2014 John Wiley & Sons, Ltd.     

Structural,morphological and steady state photoluminescence spectroscopy studies of red Eu3+‐doped Y2O3 nanophosphors prepared by the sol‐gel method

Europium trivalent (Eu³⁺)‐doped Y₂O₃ nanopowders of different concentrations (0.5, 2.5, 5 or 7 at.%) were synthesized by the sol‐gel method, at different pH values (pH 2, 5 or 8) and annealing temperatures (600°C, 800°C or 1000°C). The nanopowders samples were characterized by X‐ray diffraction (XRD), field emission scanning electron microscopy (FE‐SEM), Fourier transform infrared spectroscopy (FT‐IR) and steady state photoluminescence spectroscopy. The effect of pH of solution and annealing temperatures on structural, morphological and photoluminescence properties of Eu³⁺‐doped Y₂O₃ were studied and are discussed. It was found that the average crystallite size of the nanopowders increased with increasing pH and annealing temperature values. The Y₂O₃:Eu³⁺ material presented different morphology and its evolution depended on the pH value and the annealing temperature. Activation energies at different pH values were determined and are discussed. Under ultraviolet (UV) light excitation, Y₂O₃:Eu³⁺ showed narrow emission peaks corresponding to the ⁵D_0–⁷F_J (J = 0, 1, 2 and 3) transitions of the Eu³⁺ ion, with the most intense red emission at 611 assigned to forced electric dipole ⁵D₀→⁷F₂. The emission intensity became more intense with increasing annealing temperature and pH values, related to the improvement of crystalline quality. For the 1000°C annealing temperature, the emission intensity presented a maximum at pH 5 related to the uniform cubic‐shaped particles. It was found that for lower annealing temperatures (small crystallite size) the CTB (charge transfer band) position presented a red shift. Copyright © 2015 John Wiley & Sons, Ltd.     

Effect of annealing on down‐conversion properties of monoclinic Gd2O3:Er3+ nanophosphors

Erbium‐doped nano‐sized Gd₂O₃ phosphor was prepared by a solution combustion method in the presence of urea as a fuel. The phosphor was characterized by X‐ray diffractometry (XRD), Fourier transform infra‐red spectroscopy, energy dispersive X‐ray analysis (EDX) and transmission electron microscopy (TEM). The results of the XRD shows that the phosphor has a monoclinic phase, which was further confirmed by the TEM results. Particle size was calculated by the Debye–Scherrer formula. The erbium‐doped Gd₂O₃ nanophosphor was revealed to have good down‐conversion (DC) properties and the intensity of phosphor could be modified by annealing. The effects of annealing at 900°C on the particle size and luminescence properties were studied and compared with freshly prepared Gd₂O₃:Er³⁺ nanoparticles. The average particle sizes were calculated as 8 and 20 nm for the freshly prepared samples and samples annealed at 900°C for 1 h, respectively. The results show that both freshly prepared and annealed Gd₂O₃:Er³⁺ have monoclinic structure. Copyright © 2014 John Wiley & Sons, Ltd.     

Combustion synthesis of blue‐emitting submicron CaAl4O7:Eu2+, Dy3+ persistence phosphor

Long persistence phosphor CaAl₄O₇: Eu²⁺, Dy³⁺ were prepared by a combustion method. The phosphors were characterized by means of X‐ray diffraction (XRD), scanning electron microscopy (SEM), decay time measurement techniques and photoluminescence spectra (PL). The CaAl₄O₇: Eu²⁺, Dy³⁺ phosphor showed a broad blue emission, peaking at 445 nm when excited at 341 nm. Such a blue emission can be attributed to the intrinsic 4f → 5d transitions of Eu²⁺ in the host lattices. The lifetime decay curve of the Dy³⁺ co‐doped CaAl₄O₇: Eu²⁺ phosphor contains a fast decay component and another slow decay one. Surface morphology also has been studied by SEM. The calculated CIE colour chromaticity coordinates was (0.227, 043). We have also discussed a possible long‐persistent mechanism of CaAl₄O₇:Eu²⁺, Dy³⁺ phosphor. All the results indicate that this phosphor has promising potential for practical applications in the field of long‐lasting phosphors for the purposes of sign boards and defence. Copyright © 2011 John Wiley & Sons, Ltd.     

Structural characterization and optical properties of Ca2MgSi2O7:Eu2+,Dy3+ phosphor by solid‐state reaction method

Ca₂MgSi₂O₇:Eu²⁺,Dy³⁺ phosphor was prepared by the solid‐state reaction method under a weak reducing atmosphere. The obtained phosphor was characterized using X‐ray diffraction (XRD), transmission electron microscopy (TEM), field emission scanning electron microscopy (FESEM), energy dispersive X‐ray spectroscopy (EDX) and Fourier transform infrared (FT‐IR) techniques. The phase structure of the Ca₂MgSi₂O₇:Eu²⁺,Dy³⁺ phosphor was akermanite type, which is a member of the melilite group. The surface morphology of the sintered phosphor was not uniform and phosphors aggregated tightly. EDX and FT‐IR spectra confirm the elements present in the Ca₂MgSi₂O₇:Eu²⁺,Dy³⁺ phosphor. Under UV excitation, a broadband emission spectrum was found. The emission spectra observed in the green region centered at 535 nm, which is due to the 4f–5d transition. The mechanoluminescence (ML) intensity of the prepared phosphor increased linearly with increases in the mechanical load. The ML spectra were similar to the photoluminescence (PL), which indicates that ML is emitted from the same emitting center of Eu²⁺ ions as PL. Copyright © 2014 John Wiley & Sons, Ltd.     

Luminescence properties of Ce-doped ZrO2 phosphors synthesized by combustion method

Zr_1−xCe_xO₂ with x = 0.005, 0.01, 0.02, and 0.03 samples were synthesized using a combustion technique. The X-ray diffraction results revealed that Ce-doped ZrO₂ nanoparticles were in a monoclinic structure up to 1 mol% Ce concentration. The increase in the Ce concentration caused more distortion in the monoclinic structure of zirconia. The samples showed a mixed phase (monoclinic + tetragonal) beyond 1 mol% Ce content. The crystallite size (D) and strain (ε) were calculated from the Williamson–Hall equation. The D decreased from 25 ± 1 to 20 ± 1 nm and ε increased from 0.03 to 0.28% with an increase in Ce concentration. Photoluminescence (PL) spectra of Zr_1−xCe_xO₂ showed emission in the blue region under an excitation wavelength of 290 nm. Zr_0.995Ce_0.005O₂ showed the highest PL intensity with an average lifetime of 0.93 μs, and the PL intensity decreased with the increase in the Ce concentration. Thermoluminescence (TL) glow curves of Zr_1−xCe_xO₂ were measured after gamma irradiation (500 Gy) with a heating rate of 5 K s⁻¹. The TL curve of Zr_0.995Ce_0.005O₂ showed two prominent peaks at 412 K (peak 1) and 600 K (peak 2). The first TL glow peak was shifted towards a higher temperature at 440 K above 1 mol% Ce concentration. Repetitive TL measurements on the same aliquot exhibited excellent repeatability. Kinetic parameters associated with the TL peaks were calculated using the curve fitting method. Peak 1 followed non-first-order kinetics. The value of the activation energy of the 440 K peak was found to be 0.95 ± 0.01 eV for Zr_0.99Ce_0.01O₂. These findings showed that Zr_1−xCe_xO₂ might be used in lighting and radiation dosimeter applications.     

Synthesis and luminescence characterization of Y2BaZnO5:RE (RE = Eu3+, Tb3+, Pr3+ and Sm3+) phosphors

Modified synthesis and luminescence of Y₂BaZnO₅ phosphors activated with the rare earths (RE) Eu³⁺, Tb³⁺, Pr³⁺ and Sm³⁺ are reported. RE₂BaZnO₅ phosphors have attracted attention because of their interesting magnetic and optical properties; and are usually prepared using a two‐step solid‐state reaction. In the first step, carbonates or similar precursors are thoroughly mixed and heated at 900°C to decompose them to oxides. To eliminate the unwanted phases like BaRE₂O₄, the resulting powders are reheated at 1100°C for a long time. We prepared Y₂BaZnO₅ phosphors activated with various activators by replacing the first step with combustion synthesis. The photoluminescence results are presented. The photoluminescence results for Eu³⁺, Tb³⁺ and Pr³⁺ are in good agreement with the literature. However, photoluminescence emission from Sm³⁺ has not been documented previously. The excitation spectrum of Eu³⁺ is dominated by a charge transfer band around 261 nm, and an additional band around 238 nm is always present, irrespective of the type of activator. The presence of this band for all these different types of activators was interpreted as host absorption.     

Low temperature-synthesized MgAl2O4:Eu3+ nanophosphors and their structural validations using density functional theory: photoluminescence,photocatalytic, and electrochemical properties for multifunctional applications

A low temperature-assisted and oxalyl dihydrazide fuel-induced combustion synthesized series of uncalcined MgAl₂O₄:Eu³⁺ nanophosphors showed an average crystallite size of ~20 nm, and bandgap energy (E_g) of 4.50–5.15 eV, and were validated using density functional theory and found to match closely with the experimental values. The photoluminescence characteristic emission peaks of Eu³⁺ ions were recorded between 480 and 680 nm. The nanophosphors excited at 392 nm showed f–f transitions assigned as ⁵D₀→⁷F_J (J = 0, 1, 2, and 3). The optimized MgAl₂O₄ phosphors had Commission Internationale de l'Eclairage coordinates in the red region, a correlated colour temperature of 2060 K, and a colour purity of 98.83%. The estimated luminescence quantum efficiency ( $\eta$) was observed to be ~63% using Judd–Ofelt analysis. Electrochemical and photocatalytic performance were explored and indicated its multifunctional applications. Therefore, MgAl₂O₄:Eu³⁺ nanophosphors could be used for the fabrication of light-emitting diodes, industrial dye degradation, and as electrodes for supercapacitor applications.     

Photoluminescence and structural analysis of trivalent europium doped MLaAl3O7 (M = Ba,Ca, Mg and Sr) nanophosphors

The solution combustion technique was used to synthesize MLaAl₃O₇ (M = Ba, Ca, Mg, and Sr) nanophosphors‐doped with Eu³⁺ using metal nitrates as precursors. The photoluminescence (PL) emission spectra exhibited three peaks at 587–591, 610–616, and 653–654 corresponding to ⁵D₀→⁷F₁, ⁵D₀→⁷F₂, and ⁵D₀→⁷F₃ transitions, respectively. Upon excitation at 254 nm, these nanophosphors displayed strong red emission with the dominant peak attributed to the ⁵D₀→⁷F₂ transition of Eu³⁺. The materials were further heated at 900 and 1050°C for 2 h to examine the consequence of temperature on crystal lattice and PL emission intensity. X‐ray diffraction (XRD) analysis proved that all the synthesized materials were of a crystalline nature. CaLaAl₃O₇ material has a tetragonal crystal structure with space group P421m. Scherer's equation was used to calculate the crystallite size of synthesized phosphors using XRD data. A Fourier transformation infrared study was used to observe the stretching vibrations of metal–oxygen bonds. Infrared peaks for stretching vibrations corresponding to lanthanum–oxygen and aluminium–oxygen bonds were found at 582 and 777 cm^–1 respectively for CaLaAl₃O₇ phosphor material. Transmission electron microscopy images were used to determine the size of particles (18–37 nm for the as‐prepared materials) and also to analyze the three‐dimensional view of these materials. The experimental data indicate that these materials may be promising red‐emitting nanophosphors for use in white light‐emitting diodes.     

Luminescence properties of green‐emitting Ca2MgSi2O7:Eu2+ phosphor by a solid‐state reaction method

A europium (Eu)‐doped di‐calcium magnesium di‐silicate phosphor, Ca₂MgSi₂O₇:Eu²⁺, was prepared using a solid‐state reaction method. The phase structure, particle size, surface morphology, elemental analysis, different stretching mode and luminescence properties were analyzed by X‐ray diffraction (XRD), transmission electron microscopy (TEM), field emission scanning electron microscopy (FESEM) with energy dispersive X‐ray spectroscopy (EDX), Fourier transform infrared (FTIR) spectroscopy, photoluminescence (PL) and mechanoluminescence (ML). The phase structure of Ca₂MgSi₂O₇:Eu²⁺ was an akermanite‐type structure, which belongs to the tetragonal crystallography with space group P4?2₁m; this structure is a member of the melilite group and forms a layered compound. The surface of the prepared phosphor was not found to be uniform and particle distribution was in the nanometer range. EDX and FTIR confirm the components of Eu²⁺‐doped Ca₂MgSi₂O₇ phosphor. Under UV excitation, the main emission peak appeared at 530 nm, belonging to the broad emission ascribed to the 4f⁶5d¹→4f⁷ transition of Eu²⁺. The ML intensity of the prepared phosphor increased linearly with increasing impact velocity. A CIE color chromaticity diagram and ML spectrum confirmed that the prepared Ca₂MgSi₂O₇:Eu²⁺ phosphor would emit green color and the ML spectrum was similar to that of PL, which indicated that ML is emitted from the same center of Eu²⁺ ions. Copyright © 2015 John Wiley & Sons, Ltd.     

Combustion synthesis and luminescence properties of SrAl2O4:Eu2+, Dy3+, Tb3+ phosphor.

Eu(2+), Dy(3+) and Tb(3+) co-doped strontium aluminate phosphor with high brightness and long afterglow was synthesized by a combustion method, using urea as a reducer. The properties of SrAl(2)O(4):Eu(2+),Dy(3+),Tb(3+) phosphor with a series of initiating combustion temperatures, urea concentrations and boric acid molar fractions were investigated. The sample at initiating combustion temperature of 600 degrees C exhibited an intense emission peak at 513 nm, in which the phosphor existed as a single-phase monoclinic structure. The experimental results showed that the optimum ratio of urea is 2.0 times higher than theoretical quantities and that the suitable molar fraction of H(3)BO(3) is 0.08. The average particle size of the phosphor was 50-80 nm and its luminescence properties were studied systematically. Compared with SrAl(2)O(4):Eu(2+),Dy(3+) phosphor, the initial luminescence brightness improved from 2.50 candela (cd)/m(2) to 3.55 cd/m(2) and the long afterglow time was prolonged from 1290 s to 2743 s.