Crystallinity and morphology dependent luminescence of Li-doped Y2−xGdxO3:Eu thin film phosphors

The influence of lithium doping on the crystallization, the surface morphology, and the luminescent properties of pulsed laser deposited Y_2−xGd_xO₃:Eu³⁺ thin film phosphors was investigated. The crystallinity, the surface morphology, and the photoluminescence (PL) of films depended highly on the Li-doping and the Gd content. The relationship between the crystalline and morphological structures and the luminescent properties was studied, and Li⁺ doping was found to effectively enhance not only the crystallinity but also the luminescent brightness of Y_2−xGd_xO₃:Eu³⁺ thin films. In particular, the incorporation of Li and Gd into the Y₂O₃ lattice could induce remarkable increase in the PL. The highest emission intensity was observed Li-doped Y_1.35Gd_0.6O₃:Eu³⁺ thin films whose brightness was increased by a factor of 4.6 in comparison with that of Li-doped Y₂O₃:Eu³⁺ thin films.     

Enhanced luminescence of GdTaO4:Eu thin-film phosphors by K doping

The effect of K⁺ ions on GdTaO₄:Eu³⁺ thin-film phosphors was investigated in order to improve their luminescent properties. The GdTaO₄:Eu_0.1, K_x thin films were synthesized by sol-gel process, and characterized through measuring their microstructure and luminescence. The results indicated that photoluminescence (PL) intensity of GdTaO₄:Eu³⁺ film was improved remarkably by K doping. There were two maxima in the curve of PL intensity against K⁺ dopant concentration, where one was improved up to 2.1 times at x = 0.001 and the other was enhanced up to 2.7 times at x = 0.05. The first maximum was regarded as the alteration of the local environment surrounding the Eu³⁺ activator by incorporation of K⁺ ions, and the second maximum was due to the flux effect. Additionally, the luminescence increased with the increase of firing temperature from 800 °C to 1200 °C.     

Improved photoluminescence of pulsed-laser-ablated Y<Subscript>1-x</Subscript>Gd<Subscript>x</Subscript>VO<Subscript>4</Subscript>:Eu<Superscript>3+</Superscript> thin film phosphors by Gd substitution

Gd-substituted Y_1-xGd_xVO₄:Eu³⁺ luminescent thin films have been grown on Al₂O₃(0001) substrates using pulsed-laser deposition. The films grown under different deposition conditions have been characterized using microstructural and luminescent measurements. The crystallinity, surface morphology, and photoluminescence (PL) of the films are highly dependent on the amount of Gd. The photoluminescence (PL) brightness data obtained from Y_1-xGd_xVO₄:Eu³⁺ films grown under optimized conditions have indicated that the PL brightness is more dependent on the surface roughness than the crystallinity of the films. In particular, the incorporation of Gd into the YVO₄ lattice could induce a remarkable increase of PL. The highest emission intensity was observed with Y_0.57Gd_0.40Eu_0.03VO₄ thin film whose brightness was increased by a factor of 2.5 and 1.9 in comparison with that of YVO₄:Eu³⁺ and GdVO₄:Eu³⁺ films, respectively. This phosphor have application to flat panel displays. PACS 78.20.-e; 78.55.-m; 78.66.-w     

Luminescent characteristics of CaTiO3:Pr thin films prepared by pulsed laser deposition method with various substrates

CaTiO₃:Pr³⁺ films were deposited on different substrates such as Al₂O₃ (0 0 0 1), Si (1 0 0), MgO (1 0 0), and fused silica using pulsed laser deposition method. The crystallinity and surface morphology of these films were investigated by XRD and SEM measurements. The films grown on the different substrates have different crystallinity and morphology. The FWHM of (2 0 0) peak are 0.18, 0.25, 0.28, and 0.30 for Al₂O₃ (0 0 0 1), Si (1 0 0), MgO (1 0 0), and fused silica, respectively. The grain sizes of phosphors grown on different substrates were estimated by using Scherrer's formula and the maximum crystallite size observed for the thin film grown on Al₂O₃ (0 0 0 1). The room temperature PL spectra exhibit only the red emission peak at 613 nm radiated from the transition of (¹D₂ → ³H₄) and the maximum PL intensity for the films grown on the Al₂O₃ (0 0 0 1) is 1.1, 1.4, and 3.7 times higher than that of the CaTiO₃:Pr³⁺ films grown on MgO (1 0 0), Si (1 0 0), and fused Sillica substrates, respectively. The crystallinity, surface morphology and luminescence spectra of thin-film phosphors were highly dependent on substrates.     

Morphology and crystalline-phase-dependent luminescence of Li-doped Gd2O3:Eu3+ thin films grown by pulsed laser deposition

Gd₂O₃:Eu³⁺ and Li-doped Gd₂O₃:Eu³⁺ luminescent thin films have been grown on Si(100) substrates using pulsed laser deposition. The films grown at different deposition conditions show different crystalline and morphology structures and luminescent characteristics. Although both cubic and monoclinic crystalline structures were observed in both Gd₂O₃:Eu³⁺ and Li-doped Gd₂O₃:Eu³⁺ films, the cubic structure becomes more dominant for Li-doped Gd₂O₃:Eu³⁺ films. The photoluminescence brightness data obtained from Li-doped Gd₂O₃:Eu³⁺ films indicate that Si(100) is a promising substrate for growth of high-quality Li-doped Gd₂O₃:Eu³⁺ thin-film red phosphor. In particular, the incorporation of Li⁺ ions into the Gd₂O₃ lattice induced a change of crystallinity and enhanced surface roughness. Two major factors to determine photoluminescence brightness for Li-doped Gd₂O₃:Eu³⁺ films were crystalline phase and surface roughness. The highest emission intensity was observed with Gd_1.84Li_0.08Eu_0.08O₃, whose brightness was a factor of 2.1 larger than that of Gd₂O₃:Eu³⁺ films. This phosphor is promising for applications in flat-panel displays. PACS 78.20.-e; 78.55.-m; 78.66.-w     

Optical properties of GdTaO4:Eu thick films prepared from a PVP-containing solution

Transparent GdTaO₄:Eu³⁺ thick films were prepared from the inorganic salt and 2-methoxyethanol solution containing polyvinylpyrrolidone (PVP) via sol-gel technique. The critical thickness of the film, i.e. the maximum thickness achievable without crack formation via non-repetitive deposition, was 0.8 μm. The effect of PVP on the morphology, crystallization behavior and optical property of the GdTaO₄:Eu³⁺ thick film was investigated. The results indicated that PVP could play an important role in the formation of transparent GdTaO₄:Eu³⁺ thick films, suppressing the stress evolution, adjusting the sol viscosity, ameliorating the crystallinity, and strengthening the covalency of Eu-O bonds. The GdTaO₄:Eu³⁺ thick films prepared with PVP exhibited a superior photoluminescence and X-ray exited luminescence, which implies that it will have promising applications in high-spatial-resolution X-ray imaging and flat panel display devices.     

Crystalline and photoluminescence characteristics of YVO4:Sm thin films grown by pulsed laser deposition under oxygen pressure

YVO₄:Sm³⁺ films were deposited on Al₂O₃ (0 0 0 1) substrates at various oxygen pressures changing from 13.3 to 46.6 Pa by using the pulsed laser deposition method. The crystallinity and surface morphology of these films were investigated by means of X-ray diffraction (XRD) and atomic force microscopy (AFM), respectively. The XRD pattern confirmed that YVO₄:Sm³⁺ film has zircon structure and the AFM study revealed that the films consist of homogeneous grains ranging from 100 to 400 nm. The room temperature photoluminescence (PL) spectra showed that the emitted radiation was dominated by a reddish-orange emission peak at 602 nm radiating from the transition of (⁴G_5/2→⁶H_7/2). The crystallinity, surface morphology, and photoluminescence spectra of thin-film phosphors were highly dependent on the deposition conditions, in particular, the substrate temperature. The surface roughness and photoluminescence intensity of these films showed similar behavior as a function of oxygen pressure.     

Highly enhanced photoluminescence and X-ray excited luminescence of Li doped Gd2O3:Eu thin films

Transparent Li-doped Gd₂O₃:Eu³⁺ thin-film phosphors were prepared by a modified sol-gel method. The effect of the Li⁺ ions on luminescent properties of the thin film was investigated. The results indicated that incorporation of Li⁺ ions into Gd₂O₃ lattice could result in a remarkable increase on photoluminescence or X-ray excited luminescence, and the strongest emission was observed from Gd_1.84Li_0.08Eu_0.08O_3−δ film, in which the intensity was increased by a factor of 1.9 or 2.3 in comparison with that of Gd_1.92Eu_0.08O₃ film. And it could be achieved the highest intensity for sintering the Gd_1.84Li_0.08Eu_0.08O_3−δ film at 700 °C. Such a temperature is much lower than the typical solid-state reaction temperature for its powder phosphors. This kind of transparent thin-film phosphors may promise for application to micro X-ray imaging system.     

The luminescent properties of CaYBO4:Ln(Ln=Eu, Tb) under UV-VUV range

The luminescent properties of CaYBO₄:Ln(Ln=Eu³⁺, Tb³⁺) were investigated under ultraviolet (UV) and vacuum ultraviolet (VUV) region. The CT band of Eu³⁺ at about 245 nm blue-shifted to 230 nm in VUV excitation spectrum; the band with the maximum at 183 nm was considered as the host lattice absorption. For the sample of CaYBO₄:0.08Tb³⁺, the bands at about 235 and 263 nm were assigned to the f-d transitions of Tb³⁺ and the CT band of Tb³⁺ was calculated according to Jφrgensen's theory. Under UV and VUV excitation, the main emission of Eu³⁺ corresponding to the ⁵D₀-⁷F₂ transition located at about 610 nm and two intense emission of Tb³⁺ from the ⁵D₄-⁷F₅ transition had been observed at about 542 and 552 nm, respectively. With the incorporation of Gd³⁺ into the host lattice of CaYBO₄, the luminescence of Tb³⁺ was enhanced while that of Eu³⁺ was decreased because of their different excitation mechanism.     

The effects of substrate temperature on the structure, morphology and photoluminescence properties of pulsed laser deposited SrAl2O4:Eu,Dy thin films

In this study, SrAl₂O₄:Eu²⁺,Dy³⁺ thin film phosphors were deposited on Si (1 0 0) substrates using the pulsed laser deposition (PLD) technique. The films were deposited at different substrate temperatures in the range of 40-700 °C. The structure, morphology and topography of the films were determined by using X-ray diffraction (XRD), atomic force microscopy (AFM), scanning electron microscopy (SEM) and high resolution transmission electron microscopy (HRTEM). Photoluminescence (PL) data was collected in air at room temperature using a 325 nm He-Cd laser as an excitation source. The PL spectra of all the films were characterized by green phosphorescent photoluminescence at ∼530 nm. This emission was attributed to 4f⁶5d¹→4f⁷ transition of Eu²⁺. The highest PL intensity was observed from the films deposited at a substrate temperature of 400 °C. The effects of varying substrate temperature on the PL intensity were discussed.     

Crystallographic and luminescent characterizations of blue-emitting BaAl2S4 : Eu electroluminescent thin films

We characterized the crystallization and luminescence of blue-emitting BaAl₂S₄ : Eu electroluminescent thin films, prepared using switching electron-beam evaporation with two targets. From the photoluminescence intensity and decay profile of the activated Eu²⁺ ions in the BaAl₂S₄ : Eu, we found that the optimum annealing conditions for preparing highly luminescent thin films are a temperature of around 900°C and an annealing time of 2 min. We analyzed the crystalline properties using cross-sectional transmission electron microscope images. Evaluation of the cathodoluminescence spectra in the cross-sections showed that the BaAl₂S₄ : Eu emitting layer was luminously inhomogeneous on the depth of the layer and that the main luminescent area was near the surface of the emitting layer. We discuss here the relationship between the crystalline and luminescent properties.     

Crystalline-phase-dependent red emission behaviors of Gd2O3:Eu3+ thin-film phosphors

Gd₂O₃:Eu³⁺ luminescent thin films have been grown on Al₂O₃(0001) substrates using pulsed-laser deposition. The films grown at different deposition conditions showed different crystalline phases, surface morphologies and luminescent characteristics. Both cubic and monoclinic crystalline phases were observed for the Gd₂O₃:Eu³⁺ films, and the crystalline structure and the surface morphology of the films were highly dependent on the oxygen pressure and substrate temperature. The cubic system showed a higher luminescence than the monoclinic system. The luminescence characteristics were strongly influenced by not only the crystalline structure but also the surface morphology of the films. The photoluminescencebrightness data obtained from Gd₂O₃:Eu³⁺ films indicate that Al₂O₃(0001) is a promising substrate for growth of high-quality Gd₂O₃:Eu³⁺ thin-film red phosphor. In particular, the Gd₂O₃:Eu³⁺ films showed a much better photoluminescence behavior than a Y₂O₃:Eu³⁺ films with the same thickness. PACS 78.20.-e; 78.55.-m; 78.66.-w     

Characteristic properties of Y2SiO5:Ce thin films grown with PLD

Three different gases (nitrogen (N₂), oxygen (O₂) and argon (Ar)) were used as background gases during the growth of pulsed laser deposition (PLD) Y₂SiO₅:Ce thin films. A Krypton fluoride laser (KrF), 248 nm was used for the PLD of the films on silicon (Si) (1 0 0) substrates. The effect of the background gases on the surface morphology, crystal growth and luminescent properties were investigated. All the experimental parameters, the gas pressure (455 mT), the substrate temperature (600 °C), the pulse frequency (8 Hz), the number of pulses (4000) and the laser fluence (1.6±0.2) J/cm² were kept constant. The only parameter that was changed during the deposition was the ambient gas species. The surface morphology and average particle sizes were monitored with scanning electron microscopy (SEM) and atomic force microscopy (AFM). X-ray diffraction (XRD) and Auger electron spectroscopy (AES) were used to determine the crystal structure and composition, respectively. Cathodo- (CL) and photoluminescence (PL) were used to measure the luminescent intensities for the different phosphor thin films. The nature of the particles, ablated on the substrate, is related to the collisions between the ejected particles and the ambient gas particles. The CL and PL intensities also depend on the particle sizes. A 144 h (coulomb dose of 1.4×10⁴ C cm⁻²) electron degradation study on the thin films ablated in the Ar gas environment resulted in a decrease in the main CL intensity peak at 440 nm and to the development of a new very broad luminescent peak spectra ranging from 400 to 850 nm due to the growth of a SiO₂ layer on the surface.     

Potential PDP phosphors with strong absorption around 172 nm: Rare earth doped NaLaP2O7 and NaGdP2O7

NaLaP₂O₇ and NaGdP₂O₇ powder samples are prepared by solid-state reactions at 750 and 600 °C, respectively, and the VUV-excited luminescence properties of Ln³⁺ (Ln=Ce, Pr, Tb, Tm, Eu) in both diphosphates are studied. Ln³⁺ ions in both hosts show analogous luminescence. For Ce³⁺-doped samples, the five Ce³⁺ 5d levels can be clearly identified. As for Pr³⁺ and Tb³⁺-doped samples, strong 4f-5d absorption band around 172 nm is observed, which matches well with Xe-He excimer in plasma display panel (PDP) devices. As a result, Pr³⁺ can be utilized as sensitizer to absorb 172 nm VUV photon and transfer energy to appropriate activators, and Tb³⁺-doped NaREP₂O₇(RE=La, Gd) are potential 172 nm excited green PDP phosphors. For Tm³⁺ and Eu³⁺-doped samples, the Tm³⁺-O²⁻ charge transfer band (CTB) is observed to be at 177 nm, but the CTB of Eu³⁺ is observed at abnormally low energy position, which might originate from multi-position of Eu³⁺ ions. The similarity in luminescence properties of Ln³⁺ in both hosts indicates certain structural resemblance of coordination environment of Ln³⁺ in the two sodium rare earth diphosphates.     

Photoluminescence investigations of Zn2SiO4 co-doped with Eu and Tb ions

Zinc silicate phosphors co-doped with Eu³⁺ ions and also with both Eu³⁺ and Tb³⁺ ions were prepared by high temperature solid state reaction in air or reducing atmosphere. The luminescence characteristics of the prepared phosphors were investigated. While in the samples prepared in air, Eu³⁺ emission was found to be dominant over Tb³⁺ emission, in the samples prepared in reducing atmosphere, intense Eu²⁺ emission at 448 nm was found to be predominant over narrow Tb³⁺ emission. Luminescence studies showed that Eu³⁺ ions occupy asymmetric sites in Zn₂SiO₄ lattice. The intense f-f absorption peak of Eu³⁺ at 395 nm observed in these phosphors suggests their potential as red emitting phosphors for near ultra-violet light emitting diodes.     

Facile patterning of luminescent GdVO4:Ln (Ln?=?Eu3+, Dy3+, Sm3+) thin films by microcontact printing process

Ordered arrays of luminescent GdVO₄:Ln (Ln = Eu³⁺, Dy³⁺, Sm³⁺) films with dot patterns have been successfully fabricated via microcontact printing method. The soft-lithography process utilizes a PDMS elastomeric mold as the stamp combined with a Pechini-type sol–gel process to produce luminescent patterns on quartz plates, in which a GdVO₄:Ln (Ln = Eu³⁺, Dy³⁺, Sm³⁺) precursor solution was employed as ink. The ordered luminescent GdVO₄:Ln patterns were revealed by optical microscopy and their microstructure, consisting of nanometer-scale particles, as demonstrated by scanning electronic microscopy observations. In addition, photoluminescence and cathodoluminescence were carried out to characterize the patterned GdVO₄:Ln (Ln = Eu³⁺, Dy³⁺, Sm³⁺) samples. Upon UV-light or electron-beam irradiation, the rare earth ions Eu³⁺, Dy³⁺, and Sm³⁺ in the crystalline GdVO₄ host show their characteristic transitions dominated by ⁵D₀–⁷F₂, ⁴F_9/2–⁶H_13/2 ,and ⁴G_5/2–⁶H_7/2, respectively. These results make the combining soft lithography with a Pechini-type sol–gel route have potential applications as rare-earth luminescent pixels for next-generation field-emission display devices.     

A comparative study of the physical properties of Sb2S3 thin films treated with N2 AC plasma and thermal annealing in N2

As-deposited antimony sulfide thin films prepared by chemical bath deposition were treated with nitrogen AC plasma and thermal annealing in nitrogen atmosphere. The as-deposited, plasma treated, and thermally annealed antimony sulfide thin films have been characterized by X-ray diffraction (XRD), energy dispersive X-ray spectroscopy, scanning electron microscopy, atomic force microscopy, UV-vis spectroscopy, and electrical measurements. The results have shown that post-deposition treatments modify the crystalline structure, the morphology, and the optoelectronic properties of Sb₂S₃ thin films. X-ray diffraction studies showed that the crystallinity of the films was improved in both cases. Atomic force microscopy studies showed that the change in the film morphology depends on the post-deposition treatment used. Optical emission spectroscopy (OES) analysis revealed the plasma etching on the surface of the film, this fact was corroborated by the energy dispersive X-ray spectroscopy analysis. The optical band gap of the films (E_g) decreased after post-deposition treatments (from 2.36 to 1.75 eV) due to the improvement in the grain sizes. The electrical resistivity of the Sb₂S₃ thin films decreased from 10⁸ to 10⁶ Ω-cm after plasma treatments.     

Low-voltage cathodoluminescence property of Li-doped Gd2−xYxO3:Eu

Cathodoluminescent (CL) spectra of Li-doped Gd_2−xY_xO₃:Eu³⁺ solid-solution (0.0?x?0.8) were investigated at low voltages (300 V-1 kV). The CL intensity is maximum for the composition of x=0.2 and gradually reduces with increasing the amount of substituted Y content. In particular, small (∼100 nm) particles of Li-doped Gd_1.8Y_0.2O₃:Eu³⁺ are obtained by firing the citrate precursors at only 650°C for 18 h. Relative red-emission intensity at 300 V of this phosphor is close to 180% in comparison with that of commercial red phosphor Y₂O₃:Eu³⁺. An increase of firing temperature to 900°C results in 400-600 nm sized spherical particles. At low voltages (300-800 V), the CL emission of 100 nm sized particles is much stronger than that of 400-600 nm sized ones. In contrast, the larger particles exhibit the higher CL emission intensity at high voltages (1-10 kV). Taking into consideration small spherical morphology and effective CL emission, Li-doped Gd_1.8Y_0.2O₃:Eu³⁺ appears to be an efficient phosphor material for low voltage field emission display.     

Eu luminescence in tellurite glasses with gold nanostructures

Luminescence properties of Eu³⁺ doped TeO₂-PbO-GeO₂ glasses containing gold nanoparticles (NPs) were investigated. The emission spectra of the samples exhibited enhancement of Eu³⁺ luminescence due to the presence of gold NPs. The emission at 614 nm, due to the Eu³⁺ hypersensitive transition ⁵D₀-⁷F₂, is much influenced by the gold NPs and increases by ≈100% for samples heat-treated at 350 °C during 41 h.     

Synthesis and luminescent properties of europium-activated Ca2SnO4 phosphors by sol-gel method

In this paper, the Ca₂SnO₄:Eu³⁺ phosphor was prepared by low-temperature sol-gel method. The influence of calcined temperature and time on structure of Ca₂SnO₄:Eu³⁺ was investigated by using X-ray powder diffraction (XRD). The experimental results show that the dried gel was crystallized to the pure orthorhombic phase after calcination at 900 °C in air for 6 h. These phosphors have displayed bright red color under a UV source. The richness of the red color has been verified by determining their color coordination from the CIE standard charts, and this red emission has been assigned to ⁵D₀→⁷F₂ electric dipole transition at 616 and 620 nm. The excellent luminescence properties make it possible as a good candidate for plasma display panel (PDP) application.