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.     

X-ray photoelectron spectroscopy analysis for undegraded and degraded Gd2O2S:Tb phosphor thin films

This paper presents the X-ray Photoelectron Spectroscopy (XPS) analysis for the undegraded and degraded Gd₂O₂S:Tb³⁺ thin film phosphor. The thin films were grown with the pulsed laser deposition (PLD) technique. XPS measurements were done on Gd₂O₂S:Tb³⁺ phosphor thin films before and after electron degradation. The XPS technique has proven the presence of Gd₂O₃ on the degraded and undegraded thin film spots. The presence of the SO₂ bonding was also detected after degradation. This clearly indicates that surface reactions did occur during prolonged electron bombardment in an oxygen atmosphere.     

The effect of oxygen pressure on the structure, morphology and photoluminescence intensity of pulsed laser deposited Gd2O2S:Tb3+ thin film phosphor

Luminescent Gd₂O₂S:Tb³⁺ phosphor thin films were grown on Si (100) substrates, using the pulsed laser deposition technique. The films were grown in 100 to 300 mTorr oxygen gas (O₂) atmospheres when the substrate temperature was kept constant at 400 or 600°C. The effect of the O₂ ambient on the structure and morphological properties of the films were analyzed using x-ray diffraction (XRD), scanning electron microscopy (SEM), and atomic force microscopy (AFM), respectively. Spherical nanoparticles deposited on the Si (100) substrates were shown to crystallize in the hexagonal structure of Gd₂O₂S. The photoluminescence (PL) spectra of all the films were characterized by a stable green emission peak with a maximum at 545 nm. Improved PL intensity was observed from the films deposited at higher oxygen pressures and higher substrate temperatures. Particles sizes of the nanoparticles deposited under the different conditions varied between 19 and 36 nm for the different samples. Smaller and more densely packet particles were produces at the higher O₂ pressures and the higher temperature.     

In situ RHEED analysis of epitaxial Gd2O3 thin films grown on Si (001)

Epitaxial Gd₂O₃ thin films were successfully grown on Si (001) substrates using a two-step approach by laser molecular-beam epitaxy. At the first step, a ～0.8 nm thin layer was deposited at the temperature of 200 ^°C as the buffer layer. Then the substrate temperature was increased to 650 ^°C and in situ annealing for 5 min, and a second Gd₂O₃ layer with a desired thickness was deposited. The whole growth process is monitored by in situ reflection high-energy electron diffraction (RHEED). In situ RHEED analysis of the growing film has revealed that the first Gd₂O₃ layer deposition and in situ annealing are the critical processes for the epitaxial growth of Gd₂O₃ film. The Gd₂O₃ film has a monoclinic phase characterized by X-ray diffraction. The high-resolution transmission electron microscopy image showed all the Gd₂O₃ layers have a little bending because of the stress. In addition, a 5–6 nm amorphous interfacial layer between the Gd₂O₃ film and Si substrate is due to the in situ high temperature annealing for a long time. The successful Gd₂O₃/Si epitaxial growth predicted a possibility to develop the new functional microelectronics devices.     

Electron beam induced green luminescence and degradation study of CaS:Ce nanocrystalline phosphors for FED applications

Green luminescence and degradation of Ce³⁺ doped CaS nanocrystalline phosphors were studied with a 2 keV, 10 μA electron beam in an O₂ environment. The nanophosphors were synthesized by the co-precipitation method. The samples were characterized using X-ray diffraction, Transmission electron microscopy, Scanning electron microscopy/electron dispersive X-ray spectroscopy and Photoluminescence (PL) spectroscopy. Cubic CaS with an average particle size of 42 ± 2 nm was obtained. PL emission was observed at 507 nm and a shoulder at 560 nm with an excitation wavelength of 460 nm. Auger electron spectroscopy and Cathodoluminescence (CL) were used to monitor the changes in the surface composition of the CaS:Ce³⁺ nanocrystalline phosphors during electron bombardment in an O₂ environment. The effect of different oxygen pressures ranging from 1 × 10⁻⁸ to 1 × 10⁻⁶ Torr on the CL intensity was also investigated. A CaSO₄ layer was observed on the surface after the electron beam degradation. The CL intensity was found to decrease up to 30% of its original intensity at 1 × 10⁻⁶ Torr oxygen pressure after an electron dose of 50 C/cm². The formation of oxygen defects during electron bombardment may also be responsible for the decrease in CL intensity.     

Preparation and luminescence properties of terbium-doped lanthanum oxide nanofibers by electrospinning

Terbium-doped lanthanum oxide (La₂O₃:Tb³⁺) nanofibers were prepared by electrospinning followed by calcination at high temperature. Thermogravimetric analyzer (TGA), field emission scanning electron microscopy (FE-SEM), X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), and photoluminescence (PL) were used to characterize the obtained fibers. The results reveal that the nanofibers have an average diameter of ca. 95±25 nm and are composed of pure La₂O₃ phase. Under the excitation of 274 nm light, the La₂O₃:Tb³⁺ nanofibers exhibit the characteristic emission resulting from the ⁵D₄→⁷F_J (J=3, 4, 5, 6) transitions of Tb³⁺ ions. And the PL emission intensity is stronger than that of their nanoparticle counterparts.     

Excitation process and photoluminescence properties of Tb and Eu ions in SnO2 and in SnO2: Porous silicon hosts

Tin oxide (SnO₂)-layers-doped terbium and europium ions are elaborated by the sol-gel method on silicon substrates. After annealing at 500 °C, the transmission electron microscopy revealed a crystallization of tin oxide.The emission properties of rare-earth in SnO₂ are studied systematically against temperature annealing and Tb³⁺ concentration. The PL spectrum is optimal after annealing at 900 °C and the corresponding photoluminescence (PL) decay is nearly exponential, showing that the sample is homogenous and the PL process can be described by two levels system.The concentration effect shows a quenching of the PL intensity for Tb³⁺ concentration above 4%. From the investigation of the decay rate from the ⁷F₅ state within terbium concentration, we show that self-quenching is insured by dipole - dipole interaction. The evolutions of both PL intensity and PL lifetime versus temperature are studied. The PL intensity and PL lifetime are enhanced by deposing SnO₂:Tb³⁺ and SnO₂:Eu³⁺ in porous silicon. We show that an efficient excitation transfer from Si nanocrystallites to RE ions can occur.     

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.     

Synthesis and characterization of light emitting Eu2O3 films on Si substrates

We have studied the optical and structural properties of Eu₂O₃ thin films grown by RF magnetron sputtering on Si substrates. The films have been annealed in O₂ ambient to improve their properties. The intensity of the photoluminescence (PL) signal detected at room temperature from the films depends on the temperature of the thermal process. The structural characterization of the films, performed by transmission electron microscopy, energy filtered transmission electron microscopy and x-ray diffraction, reveals that annealing processes performed at temperatures higher than 900 °C induce a mixing at the Eu₂O₃–Si interface, leading to the formation of a silicate-like layer, which is responsible for the observed decrease of the PL intensity.     

Photoluminescence, FTIR and X-ray diffraction studies on undoped and Al-doped ZnO thin films grown on polycrystalline α-alumina substrates by ultrasonic spray pyrolysis

Undoped and aluminum-doped zinc oxide (ZnO) thin films have been grown on polycrystalline α-alumina substrates by ultrasonic spray pyrolysis (USP) technique using zinc acetate dihydrate and aluminum chloride hexahydrate (Al source) dissolved in methanol, ethanol and deionized water. A number of techniques, including X-ray diffraction (XRD), scanning electron microscopy (SEM), Fourier transform infrared (FTIR) spectroscopy, and photoluminescence (PL) were used to characterize the obtained ZnO thin films. It was seen that the orientation changed with increase in substrate temperature. During the ZnO deposition Zn source reacted with polycrystalline α-Al₂O₃ substrate to form an intermediate ZnAl₂O₄ spinel layer. It has been interestingly found that the intensity of green emission at 2.48 eV remarkably increased when the obtained ZnO:Al films were deposited at 380 °C. The FTIR absorbance intensity of spectroscopic band at 447±6 cm⁻¹ is very sensitive to oxygen sublattice disorder resulting from non-stoichiometry, which is consistent with the result of PL characterization.     

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     

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.     

Microstructural studies of bulk and thin film GDC

Ceria rare earth solid solutions are known as solid electrolyte with potential application in oxygen sensors and solid oxide fuel cells. We report the preparation of gadolinia-doped ceria, Ce_0.90Gd_0.10O_1.95, by the conventional solid-state reaction method and the preparation of thin films from a sintered pellet of gadolinia-doped ceria by the pulsed laser deposition technique. The effect of process conditions, such as substrate temperature, oxygen partial pressure, and laser energy on microstructural properties of these films are examined using powder X-ray diffraction, scanning electron microscopy, atomic force microscopy, and Raman spectroscopy.     

Effects of SnO2 surface coating on the degradation of ZnS thin film phosphor

Pulsed laser deposited ZnS bare and SnO₂ coated ultra thin films were subjected to prolonged electron beam bombardment with 2 keV energy and a steady 44 mA/cm² current density, in 1 × 10⁻⁶ Torr O₂ pressure backfilled from a base pressure of 3 × 10⁻⁹ Torr at room temperature. Auger electron spectroscopy (AES) was used to monitor changes of the surface chemical composition of both the bare and coated phosphor films during electron bombardment. Degradation was manifested by the decrease of sulphur and accumulation of oxygen on the surface of the bare phosphor. However, with the SnO₂ coating this phenomenon was delayed until the protective SnO₂ was depleted on the surface through dissociation and reduction.     

Luminescence enhancement by the reduction–oxidation synthesis in monoclinic RE2O3 (RE=Eu,Gd) phosphors containing Eu3+ activator

A novel synthesis was developed for enhanced luminescence in sesquioxide phosphors containing Eu³⁺ activator. It consisted of two annealing steps: reduction under vacuum with gaseous H₂ at 10 Torr and 1300 °C and re-oxidation at 300–1500 °C in air. The integrated luminescence intensity of the monoclinic Eu₂O₃ phosphor was enhanced ca. 21 times by this method compared with conventional processing. The photoluminescence (PL) intensity was maximized at re-oxidation temperatures of 500–1100 °C. The PL characteristics of monoclinic Eu₂O₃ and Gd₂O₃:0.06Eu samples were compared with a commercial cubic Y₂O₃:Eu phosphor. The evolution of physical characteristics during the two-step annealing was studied by Raman spectroscopy, XPS, XRD, PL decay analysis, and SEM. PL decay lifetime increased proportionally to the PL intensity over the range 0.5–100 μs. Additional vibrational modes appeared at 490, 497, and 512 cm^?1 after the two-step annealing. The increase in PL intensity was ascribed to the formation of excess oxygen vacancies and their redistribution during annealing. Resonance crossovers between the charge transfer state and the emitting ⁵D_J states are discussed in relation to reported luminescence saturation mechanisms for oxysulfides Ln₂O₂S:Eu³⁺ (Ln=Y, La).     

Morphology-dependent luminescence behavior of Y<Subscript>2-x</Subscript>Gd<Subscript>x</Subscript>O<Subscript>3</Subscript>:Eu<Superscript>3+</Superscript> thin-film phosphors grown by a laser ablation

Y_2-xGd_xO₃:Eu³⁺ luminescent thin films have been grown on Al₂O₃(0001) substrates using pulsed laser deposition. Films grown under different deposition conditions have been characterized using microstructural and luminescence measurements. The crystallinity, surface morphology and photoluminescence (PL) of the films are highly dependent on the amount of Gd present. The photoluminescence (PL) brightness data obtained from Y_2-xGd_xO₃:Eu³⁺ films grown under optimized conditions have indicated that Al₂O₃(0001) is one of the most promising substrates for the growth of high-quality Y_2-xGd_xO₃:Eu³⁺ thin-film red phosphors. In particular, the incorporation of Gd into the Y₂O₃ lattice could induce a remarkable increase of PL. The highest emission intensity was observed with Y_1.35Gd_0.60Eu_0.05O₃, whose brightness was increased by a factor of 3.1 in comparison with that of Y₂O₃:Eu³⁺ films. This phosphor may be promising for application in flat-panel displays. PACS 78.20.-e; 78.55.-m; 78.66.-w     

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.     

Luminescence mechanism of ZnO thin film investigated by XPS measurement

The effects of annealing environment on the luminescence characteristics of ZnO thin films that were deposited on SiO₂/Si substrates by reactive RF magnetron sputtering were investigated by X-ray photoelectron spectroscopy (XPS) and photoluminescence (PL). An analysis of the O 1s peak of ZnO film revealed that the concentration of oxygen vacancies increased with the annealing temperature from 600 °C to 900 °C under an ambient atmosphere. The PL results demonstrated that the intensity of green light emission at 523 nm also increased with temperature. Under various annealing atmospheres, the analyses of PL indicated that only one emission peak (523 nm) was obtained, indicating that only one class of defect was responsible for the green luminescence. The green light emission was strongest and the concentration of oxygen vacancies was highest when the ZnO film was annealed in ambient atmosphere at 900 °C. The results in this investigation show that the luminescence mechanism of the emission of green light from a ZnO thin film is associated primarily with oxygen vacancies. PACS 81.15.Cd; 81.40.Ef; 78.55.-m; 78.55.Et     

Synthesis,studies and luminescent properties of terbium oxide-doped LaMn0.9Zn0.1O3+d nanoperovskite by sol–gel method

In this research, we report on the characterization of La_1?xTb_xMn_0.9Zn_0.1O_3+d (LTMZ) (0.0≤x≤0.32). Nanoparticles with high surface area were synthesized by the polymerized complex method based on the Pechini-type reaction. High-quality nanopowders with controlled stochiometry and microstructure were prepared in the temperature range of 700–800 °C for 6 h, with mean particle sizes of approximately 18.35 nm.

The synthesized materials were characterized by X-ray powder diffraction, fourier transform infrared spectrometry and photoluminescence (PL). PL measurements showed the characteristic green emission of Tb³⁺ ions in crystalline LTMZ powders due to the ⁵D ₄→⁷F _J transitions of the 4f electrons of Tb³⁺ ions. The structure, homogeneity and particle size of the obtained compounds during different stages were investigated by scanning electron microscopy.     

Excitation and emission processes of Tb in porous anodic alumina

The strong photoluminescence (PL) of porous anodic alumina (PAA) with terbium deposition is reported. PAA, which has a regular pore morphology, is considered an effective template for fabricating luminescent composites. Tb was deposited onto PAA films by immersion in alcoholic solution with terbium chloride followed by heat treatment. The PL spectra demonstrate typical bands of Tb³⁺ corresponding to ⁵D₄ → ⁷F_j (j = 3, 4, 5, 6,) electron transition, with the maximum at 18,360 cm⁻¹ (⁵D₄ → ⁷F₅). The PL mechanism of Tb³⁺ was systematically studied with annealing temperature. The non-radiative relaxation channel is provided by OH hydroxyls at the surface of porous anodic alumina and, after annealing at 900 °C, the PL yield is highly improved. The PL intensity of Tb³⁺ increases with laser power and a saturation phenomenon, associated with the ratio of Tb³⁺ to Tb⁴⁺ ions, is observed at approximately 90 W/cm². Based on a theoretical model, the optical cross-section σ of terbium in PAA is estimated, with a value close to that of other porous materials doped with the rare-earth elements.