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.     

Synthesis of Gd2Ti2O7:Eu, V phosphors by sol-gel process and its luminescent properties

A red-emitting phosphor material, Gd₂Ti₂O₇:Eu³⁺, V⁴⁺, by added vanadium ions is synthesized using the sol-gel method. Phosphor characterization by high-resolution transmission electron microscopy shows that the phosphor possesses a good crystalline structure, while scanning electron microscopy reveals a uniform phosphor particle size in the range of 230-270 nm. X-ray photon electron spectrum analysis demonstrates that the V⁴⁺ ion promotes an electron dipole transition of Gd₂Ti₂O₇:Eu³⁺ phosphors, causing a new red-emitting phenomenon, and CIE value shifts to x=0.63, y=0.34 (a purer red region) from x=0.57, y=0.33 (CIE of Gd₂Ti₂O₇:Eu³⁺). The optimal composition of the novel red-emitting phosphor is about 26% of V⁴⁺ ions while the material is calcinated at 800  °C. The results of electroluminescent property of the material by field emission experiment by CNT-contained cathode agreed well with that of photoluminescent analysis.     

Auger electron/X-ray photoelectron and cathodoluminescent spectroscopic studies of pulsed laser ablated SrAl2O4:Eu,Dy thin films

Auger electron/X-ray photoelectron and cathodoluminescent (CL) spectroscopic studies were conducted on pulsed laser deposited SrAl₂O₄:Eu²⁺,Dy³⁺ thin films and the correlation between the surface chemical reactions and the decrease in the CL intensity was determined. The Auger electron and the CL data were collected simultaneously in a vacuum chamber either maintained at base pressure or backfilled with oxygen gas. The data were collected when the films were irradiated for 14 h with 2 keV electrons. The CL emission peak attributed to the 4f⁶5d¹ → 4f⁷ transitions was observed at ∼521 nm and the CL intensity of the peaks degraded at different rates in different vacuum conditions. X-ray photoelectron spectroscopy (XPS) data collected from degraded films suggest that strontium oxide (SrO) and aliminium oxide (Al₂O₃) were formed on the surface of the film as a result of electron stimulated surface chemical reaction (ESSCR).     

The effect of different gas atmospheres on luminescent properties of pulsed laser ablated SrAl2O4:Eu,Dy thinfilms

SrAl₂O₄:Eu²⁺,Dy³⁺ thin films were grown on Si (1 0 0) substrates using the pulsed laser deposition (PLD) technique to investigate the effect of vacuum, oxygen (O₂) and argon (Ar) deposition atmospheres on the structural, morphological, photoluminescence (PL) and cathodoluminescence (CL) properties of the films. The films were ablated using a 248 nm KrF excimer laser. Atomic force microscopy (AFM), scanning electron microscopy (SEM), X-ray diffraction (XRD), energy dispersive X-ray spectroscopy (EDS) and fluorescence spectrophotometry were used to characterize the thin films. Auger electron spectroscopy (AES) combined with CL spectroscopy were employed for the surface characterization and electron-beam induced degradation of the films. Better PL intensities were obtained from the unannealed films prepared in Ar and O₂ atmospheres with respect to those prepared in vacuum. A stable green emission peak at 515 nm, attributed to 4f⁶5d¹→4f⁷ Eu²⁺ transitions were obtained with less intense peaks at 619 nm, which were attributed to transitions in Eu³⁺. 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 CL intensity increased under prolonged electron bombardment during the removal of C due to electron stimulated surface chemical reactions (ESSCRs) on the surface of the SrAl₂O₄:Eu²⁺, Dy³⁺ thin films. The CL stabilized and stayed constant thereafter.     

XPS analysis for degraded Y2SiO5:Ce phosphor thin films

X-ray photoelectron spectroscopy (XPS) results were obtained for standard Y₂SiO₅:Ce phosphor powders as well as undegraded and 144 h electron degraded Y₂SiO₅:Ce pulsed laser deposited (PLD) thin films. The two Ce 3d peaks positioned at 877.9 ± 0.3 and 882.0 ± 0.2 eV are correlated with the two different sites occupied by Ce in the Y₂SiO₅ matrix. Ce replaced the Y in the two different sites with coordination numbers of 9 and 7. The two Ce 3d XPS peaks obtained during the thin film analysis were also correlated with the luminescent mechanism of the broad band emission spectra of the Y₂SiO₅:Ce X₁ phase. These two different sites are responsible for the two main sets of cathodoluminescent (CL) and photoluminescence (PL) peaks situated at wavelengths of 418 and 496 nm. A 144 h electron degradation study on the Y₂SiO₅:Ce thin film yielded an increase in the CL intensity with a second broad emission peak emerging between 600 and 700 nm. XPS analysis showed the presence of SiO₂ on the surface that formed during prolonged electron bombardment. The electron stimulated surface chemical reaction (ESSCR) model is used to explain the formation of this luminescent SiO₂ layer.     

Effect of Eu,Tb codoping on the luminescent properties of Y2O3 nanorods

Red-emitting Y₂O₃:Eu³⁺ and green-emitting Y₂O₃:Tb³⁺ and Y₂O₃:Eu³⁺, Tb³⁺ nanorods were synthesized by hydrothermal method. Their structure and micromorphology have been analyzed by X-ray powder diffraction (XRD) and transmission electron microscopy (TEM). The photoluminescence (PL) property of Y₂O₃:Eu³⁺,Tb³⁺ phosphor was investigated. In the same host (Y₂O₃), upon excitation with ultraviolet (UV) irradiation, it is shown that there are strong emissions at around 610 and 545 nm corresponding to the forced electric dipole ⁵D₀-⁷F₂ transition of Eu³⁺ and ⁵D₄-⁷F₅ transition of Tb³⁺, respectively. Different qualities of Eu³⁺and Tb³⁺ ions are induced into the Y₂O₃ lattice. From the excitation spectrum, we speculate that there exists energy transfer from Tb³⁺ to Eu³⁺ ions .The emission color of powders reveals regular change in the separation of light emission. These powders can meet with the request of optical display material for different colors or can be potentially used as labels for biological molecules.     

Photoluminescence properties and effects of dopant concentration in Bi2ZnB2O7:Tb phosphor

A novel green phosphor, Tb³⁺ doped Bi₂ZnB₂O₇ was synthesized by conventional solid state reaction method. The phase of synthesized materials was determined using the XRD, DTA/TG and FTIR. The photoluminescence characteristics were investigated using spectrofluorometer at room temperature. Bi₂ZnB₂O₇:Tb³⁺ phosphors excited by 270 nm and 485 nm wavelengths. The emission spectra were composed of three bands, in which the dominated emission of green luminescence Bi₂ZnB₂O₇:Tb³⁺ attributed to the transition ⁵D₄ → ⁷F₅ is centered at 546 nm. The dependence of the emission intensity on the Tb³⁺ concentration for the Bi_2−xTb_xZnB₂O₇ (0.01 ≤ x ≤ 0.15) was studied and observed that the optimum concentration of Tb³⁺ in phosphor was 13 mol% for the highest emission intensity at 546 nm.     

Low thermal quenching and high-efficiency Ce, Tb-co-doped Ca3Sc2Si3O12 green phosphor for white light-emitting diodes

Low thermal quenching and high-efficiency Ca₃Sc₂Si₃O₁₂:Ce³⁺ (CSSO:Ce³⁺) phosphors with co-doping Tb³⁺ ion were prepared by a solid state method and the properties of these phosphors were investigated. The results showed that co-doping of Tb³⁺ not only enhances the photoluminescence remarkably and decreases the thermal quenching of the phosphor, but also heightens the performances of the LEDs fabricated with the phosphor. A high-efficiency and low color temperature white LED was fabricated with the prepared CSSO:1%Ce³⁺, 0.5%Tb³⁺ and a red phosphor, indicating that CSSO:1%Ce³⁺,0.5%Tb³⁺ phosphor is a suitable green phosphor for the fabrication of high-efficiency white LEDs.     

Emission analysis of Pr and Tm: Ca2Gd2W3O14 phosphors

5 mol% of Pr³⁺ and Tm³⁺ ions activated calcium gadolinium tungstate (Ca₂Gd₂W₃O₁₄₎ phosphors were synthesized by traditional solid state reaction method. Crystalline phase structure was identified from the X-ray diffraction (XRD) profiles. From the scanning electron microscopy (SEM) images, we have observed the agglomeration of the particles, and average grain size is around 40-300 nm. Using the energy dispersive X-ray analysis (EDAX) and Fourier transform infrared (FTIR) spectra, identified the elements and functional groups present in the prepared phosphors. The emission spectrum of Pr³⁺: Ca₂Gd₂W₃O₁₄ powder phosphors have shown an intense red emission at 615 nm with the excitation wavelength λ_exci=450 nm and thus these red color emitting powder phosphors are used as one of the components in the preparation of WLEDs. The excitation spectrum of Tm³⁺: Ca₂Gd₂W₃O₁₄ powder phosphor has shown a ligand to metal charge transfer (W-O) band (LMCT) within the WO₄²⁻ group. Emission spectrum of Tm³⁺: Ca₂Gd₂W₃O₁₄ phosphors have shown blue emissions at 453 nm (¹D₂→³F₄).     

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.     

Preparation and optical properties of ZnGa2O4:Cr thin films derived by sol-gel process

ZnGa₂O₄:Cr³⁺ thin films with bright red emission were synthesized using a sol-gel process, characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD), Auger electron spectroscopy (AES) and UV-vis and fluorescence spectrophotometry measurements. Effects of calcining temperature, film thickness, calcining duration and substrates on the crystal structure and photoluminescent property have been investigated. It is found that the crystallinity, Ga/Zn ratio and band gap energy (E_g) are significant factors influencing optical characteristics, while the nature of substrates affect the surface morphologies of ZnGa₂O₄:Cr³⁺ thin films.     

Fabrication, structure and luminescence properties of polycrystalline Tb-doped Lu2SiO5 films by Pechini sol–gel method

Tb³⁺-doped lutetium oxyorthosilicate (Tb:Lu₂SiO₅, LSO) films have been successfully fabricated on carefully cleaned silicon (1 1 1) substrates by Pechini sol–gel method combined with the spin-coating technique. X-ray diffraction (XRD), photoluminescence (PL) spectra and atomic force microscopy (AFM) were employed to characterize the resultant films. XRD patterns indicated that the films were crystallized into A-type LSO phase at 1000 °C, followed by a phase transition from A-type LSO to B-type LSO occurred at 1100 °C. The AFM observation revealed that the phosphor films were uniform and crack-free, consisting of closely packed grains with an average size of 200–300 nm. The PL spectra showed the characteristic emission ⁵D₄ → ⁷F_J (J = 3–6) for Tb³⁺, The lifetime of Tb³⁺ in Tb:LSO films was 2.33 ms. The effect of heat-treatment temperature on the luminescent properties was also investigated.     

The influence of the number of pulses on the morphological and photoluminescence properties of SrAl2O4:Eu,Dy thin films prepared by pulsed laser deposition

The current work reports on the influence of the number of laser pulses on the morphological and photoluminescence properties of SrAl₂O₄:Eu²⁺,Dy³⁺ thin films prepared by the pulsed laser deposition (PLD) technique. Atomic force microscopy (AFM) was used to study the surface topography and morphology of the films. The AFM data showed that the film deposited using a higher number of laser pulses was packed with a uniform layer of coarse grains. In addition, the surface of this film was shown to be relatively rougher than the films deposited at a lower number of pulses. Photoluminescence (PL) data were collected using the Cary Eclipse fluorescence spectrophotometer equipped with a monochromatic xenon lamp. An intense green photoluminescence was observed at 517 nm from the films prepared using a higher number of laser pulses. Consistent with the PL data, the decay time of the film deposited using a higher number of pulses was characteristically longer than those of the other films. The effects of laser pulses on morphology, topography and photoluminescence intensity of the SrAl₂O₄:Eu²⁺,Dy³⁺ thin films are discussed.     

Cathodoluminescence degradation of PLD thin films

The cathodoluminescence (CL) intensities of Y₂SiO₅:Ce³⁺, Gd₂O₂S:Tb³⁺ and SrAl₂O₄:Eu²⁺,Dy³⁺ phosphor thin films that were grown by pulsed laser deposition (PLD) were investigated for possible application in low voltage field emission displays (FEDs) and other infrastructure applications. Several process parameters (background gas, laser fluence, base pressure, substrate temperature, etc.) were changed during the deposition of the thin films. Atomic force microscopy (AFM) was used to determine the surface roughness and particle size of the different films. The layers consist of agglomerated nanoparticle structures. Samples with good light emission were selected for the electron degradation studies. Auger electron spectroscopy (AES) and CL spectroscopy were used to monitor changes in the surface chemical composition and luminous efficiency of the thin films. AES and CL spectroscopy were done with 2 keV energy electrons. Measurements were done at 1×10⁻⁶ Torr oxygen pressure. The formation of different oxide layers during electron bombardment was confirmed with X-ray photoelectron spectroscopy (XPS). New non-luminescent layers that formed during electron bombardment were responsible for the degradation in light intensity. The adventitious C was removed from the surface in all three cases as volatile gas species, which is consistent with the electron stimulated surface chemical reaction (ESSCR) model. For Y₂SiO₅:Ce³⁺ a luminescent SiO₂ layer formed during the electron bombardment. Gd₂O₃ and SrO thin films formed on the surfaces of Gd₂O₂S:Tb³⁺ and SrAl₂O₄:Eu²⁺,Dy³⁺, respectively, due to ESSCRs.     

Synthesis and characterization of monodisperse spherical core-shell structured SiO2@Y3Al5O12:Ce3+/Tb3+ phosphors for field emission displays

Nanocrystalline Y₃Al₅O₁₂: Ce³⁺/Tb³⁺ (average crystalline size 30 nm) phosphor layers were coated on non-aggregated, monodisperse and spherical SiO₂ particles by the sol-gel method, resulting in the formation of core-shell structured SiO₂@Y₃Al₅O₁₂:Ce³⁺/Tb³⁺ particles. X-ray diffraction, Fourier transform infrared spectroscopy, transmission electron microscopy, photoluminescence, cathodoluminescence spectra, as well as lifetimes were utilized to characterize the core-shell structured SiO₂@Y₃Al₅O₁₂:Ce³⁺/Tb³⁺ phosphor particles. The obtained core-shell structured phosphors consist of well-dispersed submicron spherical particles with a narrow size distribution. The thickness of the Y₃Al₅O₁₂:Ce³⁺/Tb³⁺ shells on the SiO₂ cores (average size about 500 nm, crystalline size about 30 nm) could be easily tailored by varying the number of deposition cycles (100 nm for four deposition cycles). Under the excitation of ultraviolet and low-voltage electron beams (1–3 kV), the core-shell SiO₂@Y₃Al₅O₁₂:Ce³⁺/Tb³⁺ particles show strong yellow-green and green emission corresponding to the 5d–4f emission of Ce³⁺ and ⁵D₄–⁷F _J (J = 6, 5, 4, 3) emission of Tb³⁺, respectively. These phosphors may have potential application in field emission displays.     

Highly water resistant surface coating by fluoride on long persistent Sr4Al14O25:Eu/Dy phosphor

A novel and efficient method of providing moisture resistance of inorganic particles such as divalent europium activated strontium aluminate phosphors (Sr₄Al₁₄O₂₅:Eu²⁺/Dy³⁺) was developed by firing the phosphor in the presence of appropriate amount of ammonium fluoride at a temperature of 600-700 °C. Scanning electron microscopy, X-ray diffraction, FT-IR, EDAX and Photoluminescence measurements were carried out to characterize the uncoated and coated samples. The pH measurements were carried out for the water resistivity measurements. The phosphor particles became coated with a moisture-impervious thin coating that did not suppress the luminescence of the phosphor and can withstand complete immersion in water for long periods of time, showing very high water resistivity.     

Cathode luminescence characteristics of ZnGa2O4 phosphor thin films with the doped activator

The zincgallate (ZnGa₂O₄) phosphor thin film was grown using RF magnetron sputtering system at various process parameters. A ZnGa₂O₄ phosphor thin film was deposited on Si(1 0 0) substrate and annealed by a rapid thermal processor (RTP). The X-ray diffractometer (XRD) patterns indicate that the Mn-doped ZnGa₂O₄ phosphor thin film shows a (3 1 1) main peak and a spinel phase. A ZnGa₂O₄ phosphor thin film has better crystallization due to increased substrate, annealing temperature and deposition time. Also the ZnGa₂O₄:Mn phosphor thin film shows green emission (510 nm, ⁴T₁→⁶A₁), and the ZnGa₂O₄:Cr phosphor thin film shows red emission (705 nm, ⁴A₂→⁴T₂).     

Low voltage electron induced cathodoluminescence degradation and surface characterization of Sr3(PO4)2:Tb phosphor

Tb³⁺-doped Sr₃(PO₄)₂ phosphor was prepared by a sol-gel combustion method. A trigonal structure having Sr and O atoms occupying two different lattice sites were obtained. Scanning Auger nanoprobe was used to analyze the morphology of the particles. Photoluminescence (PL) and cathodoluminescence (CL) properties of Sr₃(PO₄)₂:Tb powder phosphors were evaluated and compared. In addition, the CL intensity degradation of Sr₃(PO₄)₂:Tb was evaluated when the powders were irradiated with a beam of electrons in a vacuum chamber maintained at an O₂ pressure of 1 × 10⁻⁶ Torr or a background pressure of 1 × 10⁻⁸ Torr O₂. The surface chemical composition of the degraded powders, analyzed by X-ray photoelectron spectroscopy (XPS), suggests that new compounds (metal oxides) of strontium and phosphorous were formed on the surface. It is most likely that these compounds contributed to the CL intensity degradation of the Sr₃(PO₄)₂:Tb phosphors. The CL properties and possible mechanism by which the new metal oxides were formed on the surface due to a prolonged electron beam irradiation are discussed.     

Luminescence studies on ZnO-P2O5 glasses doped with Gd2O3:Eu nanoparticles and Eu2O3

Zinc phosphate glasses doped with Gd₂O₃:Eu nanoparticles and Eu₂O₃ were prepared by conventional melt-quench method and characterized for their luminescence properties. Binary ZnO-P₂O₅ glass is characterized by an intrinsic defect centre emission around 324 nm. Strong energy transfer from these defect centres to Eu³⁺ ions has been observed when Eu₂O₃ is incorporated in ZnO-P₂O₅ glasses. Lack of energy transfer from these defect centres to Eu³⁺ in Gd₂O₃:Eu nanoparticles doped ZnO-P₂O₅ glass has been attributed to effective shielding of Eu³⁺ ions from the luminescence centre by Gd-O-P type of linkages, leading to an increased distance between the luminescent centre and Eu³⁺ ions. Both doped and undoped glasses have the same glass transition temperature, suggesting that the phosphate network is not significantly affected by the Gd₂O₃:Eu nanoparticles or Eu₂O₃ incorporation.     

节能灯用BaMgAl10O17:Eu2+,Mn2+荧光粉的劣化机理研究

对节能灯用BaMgAl₁₀O₁₇: Eu²⁺,Mn²⁺荧光粉的热劣化和紫外辐照劣化机理进行了对比研究. 发现热处理和紫外辐照处理均对BaMgAl₁₀O₁₇: Eu²⁺,Mn²⁺产生明显的发光劣化作用. 研究结果表明：热劣化主要涉及到Eu²⁺ 的氧化及其格位偏移, 而紫外辐照劣化与上述过程无关. 紫外辐照劣化主要源自高能紫外辐照使Eu²⁺ 处于更加不稳定的状态, 从而降低Eu²⁺ 的直接吸收和发射强度.