5d→4f transition in halosulphate phosphors

The synthesis, X-ray diffraction and photoluminescence characteristics in alkaline halosulphate phosphors, such as KZnSO₄Cl:Ce; KMgSO₄Cl:Ce; NaMgSO₄F:Ce and Na₃SO₄F:Ce is reported in this paper. The Ce³⁺ emission in KMgSO₄Cl:Ce phosphor is maximum and it may be useful for scintillation applications.     

Luminescence investigations on sulfate apatite Na6(SO4)2FCl:RE (RE=Dy, Ce or Eu) phosphors

A new phosphor in the Cl-F system doped with Dy, Ce and Eu has been reported. Characterization of this phosphor using XRD, PL and TL techniques is described. Polycrystalline Na₆(SO₄)₂FCl:Dy; Na₆(SO₄)₂FCl:Ce and Na₆(SO₄)₂FCl:Eu phosphors prepared by a solid state diffusion method have been studied for their X-ray diffraction, photoluminescence (PL) and thermoluminescence (TL)characteristics. The PL excitation and emission spectra of phosphors were obtained. Dy³⁺ emission in the host at 475 and 570 nm is observed due to ⁴F_9/2→⁶H_15/2 and ⁴F_9/2→⁶H_13/2 transition, respectively, whereas the PL emission spectra of Na₆(SO₄)₂FCl:Ce phosphor shows the Ce³⁺ emission at 322 nm due to 5d→4f transition of Ce³⁺ ion. In Na₆(SO₄)₂FCl:Eu lattice, Eu²⁺ as well as Eu³⁺ emissions are observed. The emission of europium ion in this compound exhibits the blue as well as red emission. The TL glow curves of the same compounds have the simple structure with a prominent peak at 150, 175 and 200 °C. TL response, fading, reusability and trapping parameters of the phosphors are also studied. The TL glow curves of γ-irradiated Na₆(SO₄)₂FCl sample show one glow peak indicating that only one set of traps is being activated within the particular temperature range each with its own value of activation energy (E) and frequency factor (s). The trapping parameters associated with the prominent glow peak are calculated using Chen’s half width method. The release of hole/electron from defect centers at the characteristic trap site initiates the luminescence process in these materials. The intensity of the TL glow peaks increases with increase of the added γ-ray dose to the samples.     

Lu2SiO5∶Ce荧光粉的热释光特性研究

采用溶胶-凝胶(Sol-Gel)技术,分别在空气中和石墨提供的弱还原气氛下制备出Lu2SiO5∶Ce0.006荧光粉。通过分析样品的结构,光致激发、发射谱和热释光谱等特性,发现弱还原气氛下制备的样品不仅光致发光强度比空气中的强,而且热释光曲线中598K处的高温热释光峰也得到了抑制。进一步考察空气中制备的Lu2SiO5∶Ce0.006,Kx(x=0.01～0.08)荧光粉,结果表明就光致发光和热释光特性而言,K+共掺杂具有与还原气氛类似的作用。综合以上两方面分析结果,可认为598K处热释光峰是由与Ce4+相关的缺陷引起的,并对K+共掺杂LSO∶Ce发光增强的原因给出了合理解释。     

Synthesis, structure and luminescence properties of Y(V,P)O4:Eu,Bi phosphors

YVO₄:Eu³⁺-based red-emitting phosphors with the compositions of Y_0.95−xVO₄:0.05Eu³⁺,xBi³⁺ (x=0.01, 0.03, 0.05, 0.07 and 0.09) and Y_0.90(V_1−zP_z)O₄:0.05Eu³⁺,0.05Bi³⁺ (z=0, 0.1, 0.3, 0.5, 0.7, 0.9 and 1.0) were synthesized by the high temperature solid-state method. The as-prepared phosphors have the similar tetragonal phase structure and their morphologies varied with the relative content ratio of V to P. The photoluminescence spectra for the as-synthesized phosphors show that a dominant red emission line at around 619 nm, which is due to the Eu³⁺ electric dipole transition of ⁵D₀-⁷F₂, is observed under different excitation wavelengths (254 and 365 nm). Further, the emission intensities of ⁵D₀-⁷F₂ transition upon 365 nm excitation increase sharply owing to the Bi³⁺ doping. Energy transfer process, luminescent lifetime and quantum efficiency for the selected Y_0.90(V_1−yP_y)O₄:0.05Eu³⁺,xBi³⁺phosphors were also studied in detail.     

Luminescence properties of CaS:Ce, Sm nanophosphors

CaS:Ce, Sm nanophosphors were synthesized via solid state diffusion method. X-Ray diffraction confirmed the cubic crystalline phase of CaS:Ce, Sm nanoparticles. The particle size calculated using Debye-Scherrer formula was found to be 52 nm. The morphological investigations of the nanoparticles were made using TEM and found to have nearly spherical morphology with diameter 45-50 nm, which is in close agreement with the XRD result. The PL emission characteristics of CaS:Ce, Sm as a function of cerium and samarium concentrations have been studied and CaS:Ce_0.6Sm_0.4 system has maximum emission intensity, hence it was opted for further studies. The CaS:Ce_0.6Sm_0.4 system showed independent emission of Sm and Ce when excited at 330 and 450 nm, respectively. To study the energy transfer between cerium and samarium, the CaS:Ce_0.6Sm_0.4 was excited at wavelengths other than the excitation wavelengths of Ce (450 nm) and Sm (330 nm). The existence of Ce emission (at an excitation of 390 nm) even in the absence of Ce excitation band and Sm emission at an excitation of 405 nm, which is the excitation band of Ce, indicates the energy transfer at these two wavelengths. Thermoluminescence characteristics of ⁶⁰Co irradiated CaS:Ce_0.6Sm_0.4 have been investigated for different doses of 0.14-125 Gy. All the glow curves show a single peak at 475 K. With increasing dose, the intensity of this peak increases and a shoulder is formed on the lower temperature side at 415 K at 21 Gy of exposure. CaS:Ce_0.6Sm_0.4 shows almost linear dose dependence up to 125 Gy.     

Synthesis and luminescence of SrZnO2 phosphors

SrZnO₂ phosphors have been synthesized by two new methods viz. carbonate decomposition at 1000 °C and combustion synthesis. Phosphors activated with Pb²⁺, Sm³⁺, Tb³⁺, Bi³⁺ and Pr³⁺ could be prepared in one step using the combustion synthesis. Characteristic emission and excitation were observed for Bi³⁺. For the remaining activators excitation spectra always contained a band at 283 nm. Presence of this band for all these different types of activators was interpreted as host sensitization.     

Thermoluminescence properties of rare earth doped lithium magnesium borate phosphors

This paper reports the thermoluminescence (TL) properties of rare earth doped lithium magnesium borate (LMB) polycrystalline phosphor. LMB phosphor has been prepared by high temperature solid state diffusion method. Among all the rare earth doped LMB phosphors, terbium doped material has shown maximum TL sensitivity with a broad dosimetric glow peak at 240 °C. near the tissue equivalent TL phosphor with terbium dopant has about four times the TL sensitivity of TLD-100. The main dosimetric properties such as glow curve stability, TL response versus absorbed dose, post-irradiation storage stability, and reusability are investigated. This TL material has a linear dose response up to 10³ Gy, negligible storage fading and a simple annealing procedure for reuse. The TL emission spectra of LMB:Tb³⁺ showed broad green emission at 544 nm, which merged with host emission. The characteristic Tb³⁺ emissions are seen in the photoluminescence (PL) spectra.     

Photoluminescence and EPR studies on gamma irradiated Ce doped potassium halide single crystals

Electron Paramagnetic Resonance(EPR), Photoluminescence(PL), Thermoluminescence (TL) and other optical studies of γ-irradiated KBr, KCl:Ce³⁺ single crystals. Cerium when doped into the KBr, KCl is found to enter the host lattice in its trivalent state and act as electron trap during γ-irradiation, thereby partially converting itself to Ce²⁺. The Photoluminescence(PL) spectra of both KCl and KBr crystals doped with Ce exhibit the strong blue emissions of Ce corresponding to ⁵d(²D)→²F_5/2 and ⁵d(²D)→²F_7/2 transitions. The defect centers formed in the Ce³⁺ doped KBr and KCl. Crystals are studied using the technique of EPR. A dominant TL glow peak at 374, 422 K and KCl:Ce³⁺ at 466, 475 K is observed in the crystal. EPR studies indicate the presence at two centers at room temperature. Spectral distribution under the thermoluminescence emission(TLE) and optically stimulated emission(OSL) support the idea that defect annihilation process to be due to thermal release of F electron in KBr, KCl:Ce³⁺ crystals. Both Ce³⁺ and Ce²⁺ emissions were observed in the thermoluminescence emission of the crystals.     

Thermo and photoluminescence properties of Eu activated hexagonal, monoclinic and cubic gadolinium oxide nanorods

Different phases of Eu³⁺ activated gadolinium oxide (Gd (OH)₃, GdOOH and Gd₂O₃) nanorods have been prepared by the hydrothermal method with and without cityl trimethyl ammonium bromide (CTAB) surfactant. Cubic Gd₂O₃:Eu (8 mol%) red phosphor has been prepared by the dehydration of corresponding hydroxide Gd(OH)₃:Eu after calcinations at 350 and 600 °C for 3 h, respectively. When Eu³⁺ ions were introduced into Gd(OH)₃, lattice sites which replace the original Gd³⁺ ions, a strong red emission centered at 613 nm has been observed upon UV illumination, due to the intrinsic Eu³⁺ transition between ⁵D₀ and ⁷F configurations. Thermoluminescence glow curves of Gd (OH)₃: Eu and Gd₂O₃:Eu phosphors have been recorded by irradiating with gamma source (⁶⁰CO) in the dose range 10-60 Gy at a heating rate of 6.7 °C sec⁻¹. Well resolved glow peaks in the range 42-45, 67-76, 95-103 and 102-125 °C were observed. When γ-irradiation dose increased to 40 Gy, the glow peaks were reduced and with increase in γ-dose (50 and 60 Gy) results the shift in first two glow peak temperatures at about 20 °C and a new shouldered peak at 86 °C was observed. It is observed that there is a shift in glow peak temperatures and variation in intensity, which is mainly attributed to different phases of gadolinium oxide. The trapping parameters namely activation energy (E), order of kinetics (b) and frequency factor were calculated using peak shape and the results are discussed.     

Synthesis and characterization of BaAl2O4:Eu co-doped with different rare earth ions

Combustion method was used in this study to prepare BaAl₂O₄:Eu²⁺ phosphors co-doped with different trivalent rare-earths (Re³⁺=Dy³⁺, Nd³⁺, Gd³⁺, Sm³⁺, Ce³⁺, Er³⁺, Pr³⁺ and Tb³⁺) ions at an initiating temperature of 600 °C. The phosphors were annealed at 1000 °C for 3 h. As confirmed from the X-ray diffraction (XRD) data, both as prepared and post annealed samples crystallized in the well known hexagonal structure of BaAl₂O₄. All samples exhibited bluish-green emission associated with the 4f⁶5d¹→4f⁷ transitions of Eu²⁺ at ∼500 nm. Although the highest intensity was observed from Er³⁺ co-doping, the longest afterglow (due to trapping and detrapping of charge carriers) was observed from Nd³⁺ followed by Dy³⁺ co-doping. The traps responsible for the long afterglow were studied using thermoluminescence (TL) spectroscopy.     

Eu3+ emission in SrAl2B2O7 based phosphors

Eu³⁺ doped SrAl₂B₂O₇ phosphors were fabricated by the wet method. The structures of the phosphors were characterized by XRD. The doping content of Eu³⁺ ions in SrAl₂B₂O₇:Eu³⁺ phosphors are 1%, 4%, 6%, 8%, 10% (molar fraction), respectively. Luminescence properties were analyzed by measuring the excitation and photoluminescence spectra. The luminescent properties of SrAl₂B₂O₇:Eu³⁺ phosphors are discussed. It is shown that from 4% to 6% of doping content of Eu³⁺ ions under 392 nm excitation in SrAl₂B₂O₇:Eu³⁺ phosphors is optimum.     

Synthesis and characterization of Eu doped SrY2O4 phosphor

The present paper reports that TL glow curve and kinetic parameter of Eu³⁺ doped SrY₂O₄ phosphor irradiated by beta source. Sample was prepared by solid state preparation method. Sample was characterized by XRD analysis and particle size was calculated by Debye–Scherrer formula. The sample was irradiated with Sr-90 beta source giving a dose of 10 Gy and the heating rate used for TL measurements are 6.7 °C/s. The samples display good TL peaks at 106 °C, 225 °C and 382 °C. The corresponding kinetic parameters are calculated. The photoluminescence excitation spectrum at 247 and 364 nm monitored with 400 nm excitation and the corresponding emission peaks at 590, 612 and 624 nm are reported.     

Luminescence characteristics of Ca1−xSrxS:Ce nanophosphors

Luminescence characteristics of Ca_1−xSr_xS:Ce (x = 0, 0.25, 0.50, 1) nanophosphors have been investigated. XRD of all the samples show a single cubic phase of Ca_1−xSr_xS:Ce. TEM micrographs exhibit the rod like structure of the samples with a decrease in diameter with decreasing amount of Ca. The results of TEM were found to be in good agreement with the XRD results. The photoluminescence spectrum comprises of a main peak in the range 480-510 nm with a shoulder in the range 530-565 nm, which may be ascribed to transitions from 5d-4f levels of cerium in the mixed host lattice. The red shift in the emission wavelength with increasing Ca content may be correlated with the change in crystal field of mixed host lattice for different Ca and Sr concentrations. We have also investigated TL response of Ca_1−xSr_x:Ce to ⁶⁰Co-γ rays. All the samples with different Sr and Ca contents show different TL response. TL response for the sample with x = 0.75 shows the simplest TL glow curve with the maximum TL intensity, for which we have calculated the activation energy using glow curve deconvolution functions.     

Energy transfer process in CaSO4:Tb,Ce phosphor

Thermoluminescence (TL) and photoluminescence studies have been carried out on CaSO₄:Tb, CaSO₄:Ce and CaSO₄:Tb,Ce phosphors with the aim of studying energy transfer process in the CaSO₄:Tb,Ce phosphor. CaSO₄:Tb,Ce shows TL peaks at 150, 220, 320 and 400°C. Changes in Tb and Ce concentrations influence the relative heights of these glow peaks. Co-doping with 0.1 mol% of Ce in CaSO₄:Tb enhances the sensitivity of 320^oC TL peak by a factor of 15. Fluorescence results show that there is energy transfer from Ce to Tb ion. The defect centres formed in CaSO₄:Tb,Ce phosphor are studied using electron spin resonance technique. The 320^oC glow peak correlates with a centre (SO₃⁻radical) with g-values: g_||=2.0061 and g_⊥=2.0026.     

Synthesis,characterization and photoluminescence of Eu3+, Ce3+ co-doped CaLaAl3O7 phosphors

Powder phosphors of CaLa_{1? x} Eu _x Al₃O₇, CaLa_{1? x} Ce _x Al₃O₇ and CaLa_{0.99? x} Eu _x Ce_0.01Al₃O₇, where x = 0.01, 0.03, 0.05 and 0.07, were prepared by a combustion method. The powders were well characterized by X-ray diffraction (XRD), scanning electron microscope (SEM) and photoluminescence techniques. Emission spectra of Eu³⁺-doped powder phosphors showed strong red emission at 613 nm (⁵D₀ → ⁷F₂); no concentration quenching was observed. Generally, Ce³⁺ acts as an efficient sensitizer when doped with other trivalent lanthanide ions. However, interestingly, in the CaLaAl₃O₇ powder phosphors, the addition of Ce³⁺ with Eu³⁺ exhibited an adverse effect–decreased photoluminescence intensity. The reasons for this behavior are discussed.     

Eu和Dy掺杂BaAl12O19长余辉发光性能研究

采用高温固相法在不同的气氛条件下合成了BaAl12O19:Eu2+/Eu3+,Dy3+发光材料。X射线衍射(XRD)表明:实验得到了纯净的BaAl12O19相结构,Eu和Dy的掺入并未改变相结构。通过比较发现,Eu和Dy掺杂后导致XRD衍射峰向高角度有微小移动,显示Eu和Dy取代晶格中Ba后使面间距发生变化。发射光谱表明:在不同条件下合成的样品都存在Eu2+的4f65d1→4f7之间的宽带跃迁;空气气氛下合成的样品中Eu2+的宽带跃迁的存在表明样品中发生了自还原现象。Dy3+的加入使样品发光增强,同时样品具备了长余辉特性。还原气氛下合成的Eu和Dy共掺样品的余辉衰减和热释光研究表明所得样品具有良好的室温和高温长余辉性能。     

Enhanced blue emission and EPR study of LaMgAl11O19:Eu phosphors

Europium doped LaMgAl₁₁O₁₉ phosphor was prepared by the combustion method. The as-prepared and post-treated (1350 °C 10 h 5% H₂+95% N₂) phosphors were investigated by X-ray diffraction (XRD), Fourier transform infrared (FT-IR), scanning electron microscopy (SEM), photoluminescence (PL) and electron paramagnetic resonance (EPR) techniques. XRD patterns show that LaMgAl₁₁O₁₉:Eu phosphors have hexagonal structure. FT-IR spectrum exhibits absorption bands corresponding to the stretching vibration of AlO₄ and AlO₆. Morphological studies reveal that this phosphor has faceted plates of varying sizes and shapes. The as-prepared LaMgAl₁₁O₁₉:Eu phosphor consists of both Eu³⁺ and Eu²⁺ ions. The phosphor exhibits a bright blue emission at 450 nm (4f⁶5d→4f⁷ transition of Eu²⁺). On post-treating the phosphor we are able to enhance the blue emission efficiency by 330%. The process was detected from the evolution of excitation, emission and EPR spectra and the results are discussed.     

Optically stimulated luminescence in doped K3Na(SO4)2 phosphors

Optically stimulated luminescence (OSL) in Cu and Eu doped K₃Na(SO₄)₂ is reported for the first time. The Cu-doped sample shows OSL sensitivity which gets enhanced by co-doping with Mg²⁺ ions. The Cu-doped and quenched sample shows better sensitivity which is almost double than that of the slowly cooled sample, whereas the sensitivity of Mg co-doped sample remains nearly same irrespective of the thermal treatment. The Cu-doped sample shows TL peak around 200 °C and moderate OSL sensitivity. Doping of Mg shifts the TL peak to around 160 °C and is correlated with good OSL sensitivity. Eu-doped sample does not show OSL sensitivity. However, relatively good OSL sensitivity is observed in Aluminium co-doped and slowly cooled sample, which is about 15% of the commercial Al₂O₃:C(Landuer Inc.). A near fully optically sensitive TL peak around 155 °C is observed. The dose response is linear and practically no OSL fading is observed in first five days of storage in slowly cooled sample. This study on conventional sulphate-based TL phosphors will be useful in developing OSL phosphors for radiation dosimetry.     

Synthesis and Eu concentration-dependent photoluminescence of Gd2−xEuxO3 nanowires

The nanowire growth behavior and photoluminescence characteristics of red-emitting oxide phosphor Gd_2−xEu_xO₃ have been investigated in the function of activator (Eu³⁺) concentrations (x=0.08, 0.12, 0.16, 0.20, and 0.24). Nanowires of Gd_2−xEu_xO₃ phosphor were prepared by the dehydration of corresponding hydroxides Gd_1−x/2Eu_x/2(OH)₃ obtained by the hydrothermal reaction. Highly uniform nanowires of 20-30 nm in diameter can grow up to several tens of micrometers in length. A number of defects on the surface of Gd_1.92Eu_0.08O₃ nanowires, which are induced during structural transformation from hexagonal hydroxide to cubic oxide, strongly decrease the luminescence efficiency in comparison with that of the bulk phosphor. In contrast, the photoemission intensity of nanowires is significantly improved with increasing Eu³⁺ content (x) of Gd_2−xEu_xO₃ solid solution. The highest relative emission intensity of nanowires is observed when the x value is close to x=0.20. This content is much higher than the optimal concentration of Eu³⁺ (x=0.08-0.10) for the bulk Gd₂O₃:Eu powder.     

A rapid combustion process for the preparation of MgSrAl10O17:Eu phosphor and related luminescence and defect investigations

Blue-emitting europium-ion-doped MgSrAl₁₀O₁₇ phosphor, prepared using the combustion method, is described. An efficient phosphor can be prepared by this method in a muffle furnace maintained at 500 °C in a very short time of few minutes. The phosphor is characterized by powder X-ray diffraction, scanning electron microscopy, transmission electron microscopy and BET surface area measurements. Photoluminescence (PL) spectra revealed that europium ions were present in divalent oxidation state. The thermoluminescence (TL) glow curve shows two peaks at around 178 and at 354 °C. The defect centres formed in the phosphor are studied using electron spin resonance (ESR). The ESR spectrum indicates the presence of Fe³⁺ ions in the non-irradiated system. Irradiated MgSrAl₁₀O₁₇:Eu exhibits lines due to radiation-sensitive Fe³⁺ ion and a defect centre. The centre is characterized by an isotropic g-value of 2.0012 and is assigned to a F⁺ centre. The radiation-sensitive Fe³⁺ ion appears to correlate with the main TL peak at 178 °C. During irradiation an electron is released from Fe²⁺ and is trapped at an anion vacancy to form F⁺ centre. During heating, an electron is liberated from the defect centre and recombines with Fe³⁺ emitting light.