Influence of Eu, Dy co-doped strontium aluminate composition on mechanoluminescence intensity

We have investigated the mechanoluminescence (ML) of Eu,Dy co-doped strontium aluminates. The SrAl₂O₄ and Sr₃Al₂O₆ indicate high ML intensity, which is clearly visible to the naked eye in the air. SrAl₂O₄:Eu,Dy shows the highest ML intensity and has many filled traps, high quantum efficiency and moderate stiffness. On the other hand, Sr₃Al₂O₆:Eu,Dy does not have many filled traps and high relative quantum efficiency, but Sr₃Al₂O₆:Eu,Dy shows relatively high ML intensity. Sr₃Al₂O₆:Eu,Dy indicates low stiffness. SrAl₄O₇:Eu,Dy has many filled traps and high relative quantum efficiency, but SrAl₄O₇:Eu,Dy shows very small ml intensity. SrAl₄O₇:Eu,Dy indicates high stiffness. This suggests that the stiffness is an important factor for the ML intensity of the Eu,Dy co-doped strontium aluminate system.     

Strong mechanoluminescence induced by elastic deformation of rare-earth-doped strontium aluminate phosphors

When rare-earth-doped strontium aluminate phosphor mixed in an epoxy resin, is deformed elastically by applying a uniaxial pressure, then initially the mechanoluminescence (ML) intensity increases with time, attains a peak value I_m at a particular time t_m, and later on it decreases with time. After t_m, initially, the ML intensity decreases exponentially at a fast rate and then it decreases exponentially at a slow rate. The ML appears after a threshold pressure and then, initially at low pressure, the peak intensity I_m of ML increases linearly with the magnitude of applied pressure, and for high pressure, I_m increases exponentially with the magnitude of applied pressure. The value of I_m increases linearly with the density of filled hole traps. The ML emission also takes place during the release of applied pressure. There should be a significant effect of temperature on the ML intensity of rare-earth-doped strontium aluminate phosphors. The ML intensity of rare-earth-doped strontium aluminates decreases with successive number of the applications of pressure and the diminished ML intensity can be recovered with the exposure of the samples to UV-radiation. The ML spectra of rare-earth-doped strontium aluminate phosphors are similar to their photoluminescence spectra. As only the piezoelectric-phase of the strontium aluminate phosphors exhibit ML during their elastic deformation, the ML emission can be attributed to the piezoelectrification of the crystals. Considering that the piezoelectric field causes decrease in the trap-depth of the hole traps and, therefore, the holes transferred from traps to the valence band recombine with (Eu¹⁺)^* ions, whereby the Eu²⁺ ions are excited, expressions are derived for different parameters of ML, which are able to satisfactorily explain the experimental results. It is shown that the lifetimes of holes in the shallow traps in stressed and unstressed materials, and the threshold pressure P_t for the ML emission, and other parameters of the ML, can be determined from the ML measurements. Finally, the criteria for tailoring strong elasico-mechanoluminescent materials are explored.     

Persistent mechanoluminescence induced by elastic deformation of ZrO2:Ti phosphors

ZrO₂:Ti phosphors show such a strong mechanoluminescence (ML) that it can be seen in day light with naked eye. When a pellet of ZrO₂:Ti phosphor mixed in epoxy resin is deformed in the elastic region at a fixed strain rate using a testing machine, ML intensity increases linearly with time, and when the deformation is stopped, ML intensity decreases exponentially with time. For a given strain rate, ML intensity increases linearly with pressure, and for a given pressure, ML intensity increases linearly with the strain rate. The total ML intensity, in the deformation region, increases quadratically with pressure; however, the total ML intensity in the post-deformation region increases linearly with pressure. ML intensity decreases with successive number of pressings, whereby the reduced ML intensity can be recovered by UV-irradiation of the sample. ML intensity increases linearly with density of filled electron traps and it is optimum for a particular concentration of Ti in ZrO₂. ML intensity should change with increasing temperature of the phosphors. Although ZrO₂ is non-piezoelectric as a whole, it seems that the local structures near the Ti ions in ZrO₂ crystals are in the piezoelectric phase. The elastico ML in ZrO₂ phosphors can be understood on the basis of the localized piezoelectrification-induced detrapping model. According to this model, the localized piezoelectric field near Ti ions causes detrapping of electrons and subsequently the detrapped electrons moving in the conduction band are captured by the energy state of excited Ti⁴⁺ ions, whereby excited Ti⁴⁺ ions are produced and consequently the decay of excited Ti⁴⁺ ions gives rise to the light emission. The expressions derived on the basis of this model are able to explain satisfactorily the characteristics of ML. The relaxation time of localized piezoelectric charges and the threshold pressure for the ML emission can be determined from ML measurements. The long decay of elastico ML indicates the possibility of exploring persistent elastico ML, which may be useful for the fabrication of dim light sources capable of operating without any external power.     

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.     

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.     

Luminescence of KCaSO4Cl:X, Y (X=Eu or Ce; Y=Dy or Mn) halosulfate material

Polycrystalline KCaSO₄Cl:Eu, Dy, KCaSO₄Cl:Ce, Dy and KCaSO₄Cl:Ce, Mn phosphors prepared by a solid state diffusion method have been studied for its photoluminescence (PL) characteristics. The presence of two overlapping bands at around 400 and 450 nm in the PL emission spectra of the phosphor suggests the presence of Eu²⁺ in the host compound occupying two different lattice sites. The effects of co-doping on the photoluminescence (PL) characteristics of KCaSO₄Cl:Eu or Ce phosphors have been studied. The decrease in peak intensity of the phosphor on co-doping it with Dy gives an insight into the emission mechanism of the phosphors, which involves energy transfer from Eu²⁺→Dy³⁺, Ce³⁺→Dy³⁺ and Ce³⁺→Mn²⁺.     

Mechanoluminescence Study of Europium Doped CaZrO<Subscript>3</Subscript> Phosphor

Behaviour displayed by mechanoluminescence (ML) in CaZrO₃:Eu³⁺ doped phosphors with variable concentration of europium ions are described. When the ML is excited impulsively by the impact of a load on the phosphors the ML intensity increases with time, attains a maximum value and then it decreases. In the ML intensity versus time curve, the peak increases and shifts towards shorter time values with increasing impact velocities. Sample was synthesized by combustion synthesis method with variable concentration of Eu³⁺ ions (0.1, 0.2, 0.5, 1, 1.5 mol%) and characterized by X-ray diffraction technique. The total ML intensity I_T is defined as the area below the ML intensity versus time curve. Initially I_T increases with impact velocity V₀ of the load and then it attains a saturation value for higher values of impact velocities which follow the relation I_T = I_T ⁰ exp.(?V_c/V₀) where I_T ⁰ and V_c are constants. Total ML intensity increases linearly with the mass of the phosphors for higher impact velocities. The ML intensity I_m, corresponding to the peak of ML intensity versus time curve increases linearly with the impact velocities. The time t_m, is found to be linearly related to 1000/V₀. The mechanoluminescence induced by impulsive excitation in europium doped CaZrO₃ phosphors plays a significance role in the understanding of biological sensors and display device application.     

Enhance luminescence by introducing alkali metal ions (R+ = Li+, Na+ and K+) in SrAl2O4:Eu3+ phosphor by solid-state reaction method

In the present article, the role of charge compensator ions (R⁺?=?Li⁺, Na⁺ and K⁺) in europium-doped strontium aluminate (SrAl₂O₄:Eu³⁺) phosphors was synthesized by the high-temperature, solid-state reaction method. The crystal structures of sintered phosphors were in a monoclinic phase with space group P2₁. The trap parameters which are mainly activation energy (E), frequency factor (s) and order of the kinetics (b) were evaluated by using the peak shape method. The calculated trap depths are in the range from 0.76 to 0.84?eV. Photoluminescence measurements showed that the phosphor exhibited emission peak with good intensity at 595?nm, corresponding to ⁵D₀–⁷F₁ (514?nm) orange emission and weak ⁵D₀–⁷F₂ (614?nm) red emission. The excitation spectra monitored at 595?nm show a broad band from 220 to 320?nm ascribed to O–Eu charge-transfer state transition and the other peaks in the range of 350–500?nm originated from f–f transitions of Eu³⁺ ions. The strongest band at 394?nm can be assigned to ⁷F₀–⁵L₆ transition of Eu³⁺ ions due to the typical f–f transitions within Eu³⁺ of 4f⁶ configuration. The latter lies in near ultraviolet (350–500?nm) emission of UV LED. CIE color chromaticity diagram and thermoluminescence spectra confirm that the synthesized phosphors would emit an orange-red color. Incorporating R⁺?=?Li⁺, Na⁺ and K⁺ as the compensator charge, the emission intensity of SrAl₂O₄:Eu³⁺ phosphor can be obviously enhanced and the emission intensity of SrAl₂O₄:Eu³⁺ doping Li⁺ is higher than that of Na⁺ or K⁺ ions.     

Photoluminescence and thermoluminescence characterization of Eu- and Dy -activated Ca3(PO4)2 phosphor

Rare-earth-doped polycrystalline Ca₃(PO₄)₂:Eu, Ca₃(PO₄)₂:Dy and Ca₃(PO₄)₂:Eu,Dy phosphors prepared by a modified solid-state synthesis has been studied for its X-ray diffraction, thermoluminescence (TL) and photoluminescence (PL) characteristics. The PL emission spectra of the phosphor suggest the presence of Eu³⁺ ion in Ca₃(PO₄)₂:Eu and Dy³⁺ ion in Ca₃(PO₄)₂:Dy lattice sites. The TL glow curve of the Ca₃(PO₄)₂:Eu compounds has a simple structure with a prominent peak at 228 °C, while Ca₃(PO₄)₂:Dy peaking at 146 and 230 °C. TL sensitivity of phosphors are compared with CaSO₄: Dy and found 1.52 and 1.20 times less in Ca₃(PO₄)₂:Eu and Ca₃(PO₄)₂:Dy phosphors, respectively. The Ca₃(PO₄)₂:Eu,Dy phosphors shows switching behavior under two different excitation wavelengths and enhancement in PL intensity of Dy³⁺ ions were reported. The paper discusses the photoluminescence and thermoluminescence behavior of Eu³⁺ and Dy³⁺ ion in Ca₃(PO₄)₂ hosts, it may be applicable to solid-state lighting as well as thermoluminescence dosimetry applications.     

Trapping mechanism in the afterglow process of the rare-earth activated Y2O2S phosphors

Phosphorescence properties are investigated in Y₂O₂S phosphors doped with rare-earth (lanthanoid, Ln) ions. Luminescence afterglow with a decay time of several ten milliseconds is observed at room temperature in the phosphors activated by Nd, Sm, Eu, Dy, Ho, Tm, Er, and Yb. The depths (thermal activation energies) of the traps causing the afterglow are measured with the transient luminescence method.It is concluded that the excited electron and the hole in the conduction and valence bands are trapped separately in the states (impurity levels) located in the vicinity of the Ln³⁺ ion. The trapping depths of the level range from 0.3 to 1.1 eV and are dependent on the electron affinity of the Ln³⁺ ion estimated from the energy difference between the 4fⁿ⁺¹ and the 4fⁿ configurations in the 4f shell of the ion.     

应力发光材料Sr2SiO4∶Eu,Dy的光谱性质研究

采用高温固相法制备一系列Sr₂SiO₄∶Eu_0.01, Dy_x(x=0.000 1, 0.002 5, 0.005, 0.01)应力发光材料,研究了不同掺杂浓度下,Sr₂SiO₄∶Eu, Dy的光致发光和应力发光性质。研究结果表明在掺杂Dy3+浓度较低时,样品同时存在α和β两种相,当掺杂Dy3+浓度增加时,则出现β到α的相转变。由于Eu2+占据Sr2+格位的不同,样品在蓝光区486 nm(Sr1)和绿光区530 nm(Sr2)有两个峰存在。而应力发光光谱与余辉光谱类似,均只呈现出530 nm的发光,这说明二者的发光来源于占据Sr2格位的Eu2+,都是通过改变陷阱的浓度实现发光性能的变化,但Sr₂SiO₄∶Eu, Dy的应力发光强度的变化还与其结构改变有关。同时,Sr₂SiO₄∶Eu, Dy应力发光强度与所施加的力之间呈良好的线性关系,并且可用眼睛观察到明显的黄色应力发光,这为应力发光传感器准确检测物体所受应力提供依据。结合余辉、热释以及应力发光性质,推测Sr₂SiO₄∶Eu, Dy的应力发光机制应是压电产生的电致发光。     

Photoluminescence of Eu single doped and Eu/Dy codoped Sr2Al2SiO7 phosphors with long persistence

This paper reports the preparation of long persistent Sr₂Al₂SiO₇:Eu²⁺ and Sr₂Al₂SiO₇:Eu²⁺, Dy³⁺ phosphors and the comparison of their photoluminescent properties. The silicate phosphors prepared by solid-state reaction routine showed a broad blue emission peaking at 484 nm when activated by UV illumination. Such a bluish-green emission can be attributed to the intrinsic 4f-5d transitions of Eu²⁺. After the UV source was switched off, long persistent phosphorescence could be observed by naked eyes for both samples in darkness. Afterglow measurements revealed that Eu/Dy codoped phosphor possesses better afterglow properties than the Eu single doped one, since the maximum lifetime (τ_max=99 s) of the photons calculated from the decay profile is much larger than that of the Eu single doped phosphor (τ_max=82 s). TSL results suggested that the difference in afterglow properties was caused by the difference in the electron traps within the crystal lattice. For Eu/Dy codoped phosphor, the doping of Dy ions produced electron traps with trap depth of 0.52 eV, which is suitable and therefore leads to good persistence. However, in the case of Eu single doped phosphor, the trap depth is 0.88 eV, which is really too deep an energy barrier to overcome, and therefore a poor persistence was observed in the experiment.     

Synthesis and luminescence properties of needle-like SrAl2O4:Eu, Dy phosphor via a hydrothermal co-precipitation method

Needle-like SrAl₂O₄:Eu²⁺, Dy³⁺ phosphors had been prepared by calcining the precursors obtained from hydrothermal process at the temperature of 1100 °C in a weak reductive atmosphere of active carbon. The crystal structure, morphology and optical properties of the composites were characterized. X-ray diffraction (XRD) patterns illustrated that the single-phase SrAl₂O₄ was formed at 1100 °C, which is much lower than that prepared by the traditional method. The transmission electron microscope (TEM) observation revealed the precursors and the resulted SrAl₂O₄:Eu²⁺, Dy³⁺ phosphors had well-dispersed distribution and needle-like morphology with an average diameter about 150 nm at the center and the length up to 1 μm. After irradiation by ultraviolet radiation with 350 nm for 5 min, the phosphors emit green color long-lasting phosphorescence corresponding to the typical emission of Eu²⁺ ion, both the PL spectra and luminance decay revealed that the phosphors had efficient luminescent and long lasting properties.     

Synthesis and luminescence properties of SrAl2O4:Eu,Dy nanosheets

We report an effective method to synthesize SrAl₂O₄:Eu²⁺,Dy³⁺ nanosheets. Sheet-like precursors were firstly synthesized by the solvothermal method, and acetate was used as the raw material. Then the final products were obtained by calcinating the precursor in a weak reductive atmosphere of H₂. The crystal structure and particle morphology were investigated by X-ray diffraction (XRD) patterns, field-emission scanning electron microscopy and transmission electron microscopy (FE-SEM and TEM) , respectively. A possible growth mechanism was proposed to reveal the formation process. Luminescence properties of the SrAl₂O₄:Eu²⁺,Dy³⁺ long-lasting phosphor were analyzed by measuring the excitation spectra, the emission spectra, the afterglow decay curve and the thermoluminescence curve. Both the photoluminescence (PL) spectra and luminance decay revealed that the phosphors had efficient luminescent and long lasting properties compared with the phosphors prepared by using nitrates as the raw material. Furthermore, the photoluminescence intensity was even a little higher than commercial phosphors.     

Luminescent properties of SrAl2B2O7: Ce, Tb

By using metal nitrates as starting materials, SrAl₂B₂O₇: Tb³⁺ and SrAl₂B₂O₇: Ce³⁺, Tb³⁺ powder phosphors were prepared by sol-gel method. X-ray diffraction (XRD), photoluminescence excitation and emission, as well as kinetic decays were employed to characterize the resulting samples. The results show that energy transfers from Ce³⁺ to Tb³⁺ ions. The emission intensity of Tb³⁺ ions in SrAl₂B₂O₇ could be greatly intensified when Ce³⁺ ions are doped into SrAl₂B₂O₇: Tb³⁺. The decay times of SrAl₂B₂O₇: Tb³⁺ were prolonged when Ce³⁺ ions were doped. The doping of Ce³⁺ ions not only improved the luminescent intensity, but also made the materials gets stable luminescent properties.     

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.     

SrAl_2B_2O_7:Dy~(3+)材料的制备及其发光性能

采用高温固相法制备了SrAl2B2O7:Dy3+发光材料.在350nm紫外光激发下,测得SrAl2B2O7:Dy3+材料的发射光谱为一个多峰宽谱,主峰分别为480,573和678nm;分别和Dy3+的4F9/2→6H15/2,4F9/2→6H13/2,4F9/2→6H11/2的跃迁发射相对应;监测573nm的发射峰,得到材料的激发光谱为一个多峰宽谱,主峰分别为295,325,350,365,400nm.研究了Dy3+掺杂浓度对SrAl2B2O7:Dy3+材料发射光谱的影响,随着Dy3+掺杂浓度的增大,SrAl2B2O7:Dy3+材料的Iy/Ib逐渐增大,根据Judd-Ofelt理论解释了其原因.随着Dy3+掺杂浓度的增大,Dy3+的4F9/2→6H13/2跃迁产生的573nm发射峰强度先增大,在4%时达到最大值,之后减小,其自身的浓度猝灭机理为电偶极-电偶极相互作用.不同的电荷补偿剂Li+,Na+,K+的引入均使发光强度得到提高,尤其以Li+最佳,发光强度提高了大约33%.     

Spectroscopy study of SrAl2O4:Eu3+

Computational and experimental method is employed to study optical properties SrAl₂O₄ induced by europium dopant. Atomistic modeling is used to predict the doping sites and charge-compensation schemes for SrAl₂O₄:Eu systems and also to calculate the symmetry and the detailed geometry of the dopant site. This information is then used to calculate the crystal field parameters. SrAl₂O₄ doped with europium were prepared via a sol–gel proteic methodology. The photoluminescence experiments were performed at room temperature and at 13 K. The transition energy for the Eu³⁺-doped material is compared to the theoretical results. Based on Judd-Ofelt approach, the intensity parameters Ω_2,4 of Eu³⁺ in the SrAl₂O₄ matrix were calculated.     

Red emission in B- and Li-doped SrAl2O4:Eu phosphor under UV excitation

Samples of SrAl₂O₄:Eu³⁺ doped with B³⁺ and SrAl₂O₄:Eu³⁺ co-doped with B³⁺ and Li⁺ have been prepared by the solid-reaction method. The influence of B³⁺ and Li⁺ contents on luminescence property has been investigated. It is found that the substitution of B³⁺ for Al³⁺ greatly improves red emission intensity at 591, 615 and 701 nm. The dopant Li⁺ as charge compensator in SrAl₂O₄:Eu³⁺, B³⁺ can further enhance luminescence intensity. The strongest red emission is obtained in the Sr(Al_1.9, B_0.1)O₄:Eu_0.02³⁺, Li⁺_0.02 sample. The developed phosphors can be efficiently excited by ultraviolet (UV) light from 350 to 480 nm, which indicates that B³⁺ and Li⁺ co-doped SrAl₂O₄:Eu³⁺ is a good candidate phosphor applied in solid-state lighting in conjunction with white UV light-emitting diodes (LEDs).