Room temperature photoluminescence from Zr-doped sol-gel silica

Intense room-temperature photoluminescence (PL) from the UV to the green region was observed from Zr⁴⁺-doped silica synthesized by a sol-gel process using tetraethoxysilane as the precursor, followed by thermal treatment at 500 °C in air. The wide PL band can be resolved into three components centered at 3.70, 3.25, and 2.65 eV, respectively. The intensity of the 3.25 and 2.65 eV PL bands was greatly enhanced compared with pure sol-gel silica. The 3.70 eV emission was assigned to non-bridging oxygen hole centers, while the 2.65 eV one originated from neutral oxygen vacancies (V_O). The 3.25 eV PL band was most likely associated with E′ centers, as supported by electron spin resonance measurement. It was proposed that the Zr⁴⁺-doping leads to oxygen deficiency in the silica, thus resulting in enhancement of the density of V_O and E′ center defects.     

Nano-star formation in Al-doped ZnO thin film deposited by dip-dry method and its characterization using atomic force microscopy, electron probe microscopy, photoluminescence and laser Raman spectroscopy

Zinc oxide doped with Al (AZO) thin films were prepared on borosilicate glass substrates by dip and dry technique using sodium zincate bath. Effects of doping on the structural and optical properties of ZnO film were investigated by XRD, EPMA, AFM, optical transmittance, PL and Raman spectroscopy. The band gap for ZnO:Al (5.0 at. wt.%) film was found to be 3.29 eV compared with 3.25 eV band gap for pure ZnO film. Doping with Al introduces aggregation of crystallites to form micro-size clusters affecting the smoothness of the film surface. Al³⁺ ion was found to promote chemisorption of oxygen into the film, which in turn affects the roughness of the sample. Six photoluminescence bands were observed at 390, 419, 449, 480, 525 and 574 nm in the emission spectra. Excitation spectra of ZnO film showed bands at 200, 217, 232 and 328 nm, whereas bands at 200, 235, 257 and 267 nm were observed for ZnO:Al film. On the basis of transitions from conduction band or deep donors (CB, Zn_i or V_OZn_i) to valence band and/or deep acceptor states (VB, V_Zn or O_i or O_Zn), a tentative model has been proposed to explain the PL spectra. Doping with Al³⁺ ions reduced the polar character of the film. This has been confirmed from laser Raman studies.     

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.     

Stimulated self-trapped exciton emission in CsI:Pb

Defects of the type of V_K and Pb⁺ centres were created in CsI:Pb under the 4.03 eV XeCl laser line irradiation at 10 K. After irradiation, the self-trapped and localized exciton emission excited by the same XeCl laser line was observed as a result of the recombination of electrons, optically released from Pb⁺, with the V_K centres. A strongly superlinear dependence of the emission intensity on the excitation intensity was found for the 3.65 eV emission of the self-trapped exciton. A much weaker superlinearity was observed for the visible localized exciton emission. Optical amplification of the exciton emission was considered as the most probable reason of the observed phenomenon. At 10 K, optical gain G=3.74 was calculated for the self-trapped exciton emission.     

Photoluminescence of Si from Si nanocrystal-doped SiO2/Si multilayered sample

A multilayered Si nanocrystal-doped SiO₂/Si (or Si-nc:SiO₂/Si) sample structure is studied to acquire strong photoluminescence (PL) emission of Si via modulating excess Si concentration. The Si-nc:SiO₂ results from SiO thin film after thermal annealing. The total thickness of SiO layer remains 150 nm, and is partitioned equally into a number of sublayers (N = 3, 5, 10, or 30) by Si interlayers. For each N-layered sample, a maximal PL intensity of Si can be obtained via optimizing the thickness of Si interlayer (or d_Si). This maximal PL intensity varies with N, but the ratio of Si to O is nearly a constant. The brightest sample is found to be that of N = 10 and d_Si = 1 nm, whose PL intensity is ∼5 times that of N = 1 without additional Si doping, and ∼2.5 times that of Si-nc:SiO₂ prepared by co-evaporating of SiO and Si at the same optimized ratio of Si to O. Discussions are made based on PL, TEM, EDX and reflectance measurements.     

Surface state density distribution at vacuum-annealed InP(1 0 0) surface as derived from the rigorous analysis of photoluminescence efficiency

The surface state density distribution N_SS(E) and surface Fermi level E_Fs position on a sequentially ultra-high vacuum-annealed n-InP(1 0 0) sample are investigated using rigorous computer analysis of dependences of the room temperature band-edge photoluminescence efficiency (Y_PL) on the photon flux density (Φ). We have found that the minimum density of a U-shaped N_SS(E) distribution as well as the donor-like surface state density are reduced by one order of magnitude after the annealing at 250 and 300 °C. This can be assigned to the decrease in the disorder in the unintentionally formed InP native oxides. On the other hand, we demonstrate that the annealing simultaneously generates discrete surface states probably due to missing group V element (P) in the interface region which may account for electrical interface instabilities observed in InP-based devices. The results are discussed quantitatively and compared to other reports.     

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.     

A novel blue magnesium strontium aluminate-based phosphor for PDP application

A novel blue light-emitting phosphor, Eu²⁺-doped magnesium strontium aluminate (MgSrAl₁₀O₁₇:Eu²⁺), for plasma display panel (PDP) application was developed. X-ray diffraction (XRD) patterns disclosed that the phosphor annealed at 1500 °C for 5 h was a pure MgSrAl₁₀O₁₇ phase. Field emission scanning electron microscopy (FE-SEM) images showed the particle size of the phosphor was less than 3 μm. The phosphor shows strong and broad blue emission under vacuum ultraviolet (VUV) light excitation. After baking at 400-600 °C and irradiation with VUV light for 300 h, the phosphor still keep excellent VUV luminescence properties exhibiting good stability against high temperature baking and VUV irradiation. The decay time was short as 1.09 μs and the quantum yield was high to 0.77±0.02. All the characteristics indicated that MgSrAl₁₀O₁₇:Eu²⁺ would be a promising blue phosphor for PDP application.     

Superconducting molybdenum nitride epitaxial thin films deposited on MgO and α-Al2O3 substrates by molecular beam epitaxy

Molybdenum nitride Mo₂N_x films were grown on MgO(0 0 1) and on α-Al₂O₃(0 0 1) substrates by molecular beam epitaxy under nitrogen radical irradiation. X-ray photoelectron spectroscopy revealed that the composition of the film varied in the range of Mo₂N_1.4-Mo₂N_2.8 depending on the growth temperature. The deposition at 973 K gave well-crystallized films on both substrates. The high-resolution reciprocal space mapping by X-ray diffraction showed that the nitrogen-rich γ-Mo₂N crystalline phase (the composition: Mo₂N_1.4) was epitaxially grown on MgO at 923 K with a slight tetragonal distortion (a = 0.421 and c = 0.418 nm) to fit the MgO lattice (a = 0.421 nm). On α-Al₂O₃(0 0 1), nitrogen-rich γ-Mo₂N (Mo₂N_1.8) was grown at 973 K with (1 1 1) planes parallel to the substrate surface. X-ray diffraction analysis with a multi-axes diffractometer revealed that the γ-Mo₂N on α-Al₂O₃(0 0 1) had a slight rhombohedral distortion (a = 0.4173(2) and α = 90.46(3)°). Superconductivity was observed below 2.8-3 K for the films grown at 973 K on MgO and on α-Al₂O₃(0 0 1).     

A new blue-emitting phosphor, SrZnO2:Pb, synthesized by the adipic acid templated sol-gel route

A new blue-emitting phosphor, Sr_1−xPb_xZnO₂, was prepared by a novel adipic acid templated sol-gel route. Photoluminescence and crystalline properties were investigated as functions of calcination temperatures and the Pb²⁺ doping levels. It was found that under UV excitation with a wavelength of 283 or 317 nm, the phosphors gave emission from 374 to 615 nm with a peak centered at 451 nm. This broad-band was composed of UV and the visible range was attributed to an impurity-trapped exciton-type emission. The maximum emission intensity of the Sr_1−xPb_xZnO₂ phosphors occurred at a Pb concentration of x=0.01. The decay time was observed to be ∼33 ms for the compound doped with 1 mol% Pb prepared at 1000 °C. Diffuse reflectance spectra revealed the characteristic absorption peaks and the bandgap energy of SrZnO₂ was found to be 3.4 eV. SEM analysis indicated that phosphor particles have an irregularly rounded morphology and the average particle size was found to be approximately 1 μm.     

Luminescence of some zirconium-containing compounds under vacuum ultraviolet excitation

Photoluminescence of compounds that contain stoichiometric zirconium has been studied under vacuum ultraviolet excitation. The compounds show emission peaking at 280-320 nm while the excitation spectra show some bands in 130-190 nm region. The ultraviolet emission is explained as Zr to O charge transfer transition. The luminescence result and structural information classify the studied compounds into two groups. The former group involves ZrP₂O₇, CaZr(PO₄)₂, NaZr₂(PO₄)₃, Ca₂ZrSi₄O₁₂, Ca₃ZrSi₂O₉ and SrZrSi₂O₇, which show rather intense luminescence and do not have any infinite Zr-O-Zr-O-3D chain or link in their structure. The latter group is CaZrO₃ and ZrSiO₄, which do contain infinite Zr-O-Zr-O-3D chain and show quite weak luminescence. Luminescence of Ca_1−xMn_xZr(PO₄)₂ has also been studied. By replacing a part of Ca with Mn, ultraviolet emission of the host weakens and visible emission peaking at 540 nm appears. It is claimed that transfer of absorbed energy from Zr to Mn occurs.     

Room-temperature electrosynthesized ZnO thin film with strong (0 0 2) orientation and its optical properties

ZnO thin film with strong orientation (0 0 2) and smooth surface morphology was electrosynthesized on ITO-coated glass substrate at room temperature under pulsed voltage. Photoluminescence (PL) shows two obvious peaks: violet band and strong green band. The former is due to the free-excitonic transition and the latter is believed to arise from the single ionized oxygen vacancy (V_O⁺). Raman scattering reveals that the 580 cm⁻¹ mode and the shoulder peak mode at 550 cm⁻¹ originate from the N-related local vibration mode (LVM) and E₁ (LO) mode, respectively.     

The morphology and optical properties of Cr-doped ZnO films grown using the magnetron co-sputtering method

Undoped ZnO and Zn_0.9Cr_0.1O films were prepared on Al₂O₃ (0 0 0 1) substrates using the magnetron co-sputtering technique. X-ray diffraction scans show that all films exhibit nearly single-phase wurtzite structure with c-axis orientation. Both chromium doping and growth ambient have a significant impact on the lattice constants and nucleation processes in ZnO film. A large quantity of subgrains (10 nm in size) has been observed on Zn_0.9Cr_0.1O film grown under Ar + O₂, while irregular plateau-like grains 40-50 nm in size were observed on Zn_0.9Cr_0.1O film grown under Ar + N₂. The ultraviolet-visible transmittance and optical bandgap of all films were also examined. The photoluminescence spectra of all films exhibit a broad emission located around 400 nm, which is composed of one weak ultraviolet luminescence and another rather intense near-violet one, as determined by Gaussian peak fitting. The near-violet emission centered on 400 nm might originate from the electron transition between the band tail state levels of surface defects and/or lattice imperfection in the ZnO film.     

Infrared superbroadband emission of Bi ion doped germanium-aluminum-sodium glass

The 96GeO-(3-χ)Al₂O₃-χNa₂O-1NaBiO₃ (χ = 0, 0.5, 1.5 molar percent designated as A1, A2 and A3) and 96GeO-(3.5-ψ)Al₂O₃-ψNa₂O-0.5Bi₂O₃ (ψ = 0.5, 1, 2 molar percent designated as B1, B2 and B3) glasses were prepared by conventional melting method with the measurement of their DTA curve, fluorescence decay curve, transmission, absorption and emission spectra. The near infrared superbroadband emission characteristics of the A1, A2, B1 and B2 glasses peak at ∼1220 nm were observed when pumped by an 800 nm laser diode. The stimulated emission cross section (σ_p) was obtained from the emission spectra. The result indicated that the introduction of Bi⁵⁺ in NaBiO₃ into raw materials could increase the emission intensity of the obtained glasses by 5.6 times than that of Bi³⁺ in Bi₂O₃, and the FWHM (Δλ) and emission lifetime (τ) at 1220 nm increased from 195 nm to 275 nm, and 280 μs to 434 μs. Meanwhile, it was found that the absorption edges were blue-shifted from 486 to 447 nm by comparing those of A1 and B1. The absorption edges were considered to be ascribed to the charge transfer from Bi³⁺ 6s² to Bi⁵⁺ 6s⁰. Therefore we could conclude that the content of Bi⁵⁺ ions in A1 was more than that in B1 glasses. It could be deduced from the emission and absorption spectra that the stronger emission intensity and wider FWHM were due to the higher concentration of Bi⁵⁺ ion in glass. In particular, the increase of Na₂O content was in proportion to the thermal stability and the value of σ_p × τ and σ_p × Δλ of glasses.     

Synthesis and luminescent properties of a new red-emitting phosphor for solid-state lighting: Eu0.1GdxLa1.9−xTeO6 (0.02?x?0.1)

The photoluminescence (PL) emission and excitation behavior of red-emitting Eu_0.1Gd_xLa_1.9−xTeO₆ (0.02?x?0.1) powder phosphors is reported. Three dominant bands centered at 395, 466 and 534 nm characterized the excitation spectrum. Under the excitation of 395 nm UV light, the emission spectrum exhibits an intense peak centered at 616 nm corresponding to the ⁵D₀→⁷F₂ transition of Eu³⁺. Because the f→f transitions are located in the wavelength range of blue or near-UV range, optimized phosphor, Eu_0.10Gd_0.08La_1.82TeO₆, is a promising material for solid-state lighting based on GaN LEDs applications.     

Stress induced preferred orientation and phase transition for ternary WCxNy thin films

We deposit ternary WC_xN_y thin films on Si (1 0 0) substrates at 500 °C using direct current (DC) reactive magnetron sputtering in a mixture of CH₄/N₂/Ar discharge, and explore the effects of substrate bias (V_b) on the intrinsic stress, preferred orientation and phase transition for the obtained films by virtue of X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), and selective area electron diffraction (SAED). We find that with increasing the absolute value of V_b up to 200 V the carbon (x) and nitrogen (y) atom concentrations of WC_xN_y films keep almost constant with the values of 0.75 and 0.25, respectively. The XPS and SAED results, combined with the density-functional theory (DFT) calculations on the electronic structure of WC_0.75N_0.25, show our obtained WC_xN_y films are single-phase of carbonitrides. Furthermore, we find that the compressive stress sharply increases with increasing the absolute value of V_b, which leads to a pronounced change in the preferred orientation and phase structure for the film, in which a phase transition from cubic β-WC_xN_y to hexagonal α-WC_xN_y occurs as V_b is in the range of −40 to −120 V. In order to reveal the relationship between the stress and phase transition as well as preferred orientation, the DFT calculations are used to obtain the elastic constants for β-WC_xN_y and α-WC_xN_y. The calculated results show that the preferred orientation is dependent on the competition between strain energy and surface energy, and the phase transition can be attributed to a decrease in the strain energy.     

Spectroscopic investigations of Nd-, Er-, Er/Yb-, and Tm-ions doped SiO2-Al2O3-CaF2-GdF3 glasses

This paper reports on the absorption, visible and near-infrared luminescence properties of Nd³⁺, Er³⁺, Er³⁺/2Yb³⁺, and Tm³⁺ doped oxyfluoride aluminosilicate glasses. From the measured absorption spectra, Judd-Ofelt (J-O) intensity parameters (Ω₂, Ω₄ and Ω₆) have been calculated for all the studied ions. Decay lifetime curves were measured for the visible emissions of Er³⁺ (558 nm, green), and Tm³⁺ (650 and 795 nm), respectively. The near infrared emission spectrum of Nd³⁺ doped glass has shown full width at half maximum (FWHM) around 45 nm (for the ⁴F_3/2→⁴I_9/2 transition), 45 nm (for the ⁴F_3/2→⁴I_11/2 transition), and 60 nm (for the ⁴F_3/2→⁴I_13/2 transition), respectively, with 800 nm laser diode (LD) excitation. For Er³⁺, and Er³⁺/2Yb³⁺ co-doped glasses, the characteristic near infrared emission bands were spectrally centered at 1532 and 1544 nm, respectively, with 980 nm laser diode excitation, exhibiting full width at half maximum around 50 and 90 nm for the erbium ⁴I_13/2→⁴I_15/2 transition. The measured maximum decay times of ⁴I_13/2→⁴I_15/2 transition (at wavelength 1532 and 1544 nm) are about 5.280 and 5.719 ms for 1Er³⁺ and 1Er³⁺/2Yb³⁺ (mol%) co-doped glasses, respectively. The maximum stimulated emission cross sections for ⁴I_13/2→⁴I_15/2 transition of Er³⁺ and Er³⁺/Yb³⁺ are 10.81×10⁻²¹ and 5.723×10^-21 cm². These glasses with better thermal stability, bright visible emissions and broad near-infrared emissions should have potential applications in broadly tunable laser sources, interesting optical luminescent materials and broadband optical amplification at low-loss telecommunication windows.     

Synthesis and luminescent properties of two Schiff-base boron complexes

Schiff bases N,N′-o-phenylenebis (salicylideneimine) (H₂L¹), N,N′-p-phenylenebis (salicylideneimine) (H₂L²) and their corresponding boron complexes (BF₂)₂L¹, (BF₂)₂L² were synthesized, respectively. The two boron complexes have been characterized by ¹H NMR, mass spectrometry and elemental analysis, while the luminescent properties of them were investigated with UV-VIS spectroscopy and photoluminescence spectroscopy. Then the three-layer devices [ITO/NPB (60 nm)/(BF₂)₂L¹ (50 nm)/Alq3 (20 nm)/LiF (1 nm)/Al (200 nm)] (device I) and [ITO/NPB (60 nm)/(BF₂)₂L² (50 nm)/Alq3 (20 nm)/LiF (1 nm)/Al (200 nm)] (device II) were fabricated by vacuum deposition. These two devices both exhibited blue green emission at 500 nm, but showed different luminances and efficiencies.     

Spectral analysis of Pr-, Sm- and Dy-doped transparent GeO2-BaO-TiO2 glass ceramics

In this paper, we present the photoluminescence properties of Pr³⁺-, Sm³⁺- and Dy³⁺-doped germanate glasses and glass ceramics. From the X-ray diffraction measurement, the host glass structure was determined. These glasses have shown strong absorption bands in the near-infrared (NIR) region. Compared to Pr³⁺-, Sm³⁺- and Dy³⁺-doped glasses, their respective glass ceramics have shown stronger emissions due to the Ba₂TiGe₂O₈ crystalline phase. For Pr³⁺-doped glass and glass ceramic, emission bands centered at 530 nm (³P₀→³H₅), 614 nm (³P₀→³H₆), 647 nm (³P₀→³F₂) and 686 nm (³P₀→³F₃) have been observed with 485 nm (³H₄→³P₀) excitation wavelength. Of them, 647 nm (³P₀→³F₂) has shown bright red emission. Emission bands of ⁴G_5/2→⁶H_5/2 (565 nm), ⁴G_5/2→⁶H_7/2 (602 nm) and ⁴G_5/2→⁶H_9/2 (648 nm) for the Sm³⁺:glass and glass ceramic, with excitation at ⁶H_5/2→⁴F_7/2 (405 nm) have been recorded. Of them, ⁴G_5/2→⁶H_7/2 (602 nm) has shown a bright orange emission. With regard to the Dy³⁺:glass and glass ceramic, a bright fluorescent yellow emission at 577 nm (⁴F_9/2→⁶H_13/2) has been observed, apart from ⁴F_9/2→⁶H_11/2 (667 nm) emission transition with an excitation at 454 nm (⁶H_15/2→⁴I_15/2) wavelength. The stimulated emission cross-sections of all the emission bands of Pr³⁺, Sm³⁺ and Dy³⁺:glasses and glass ceramics have been computed based on their measured full-width at half-maxima (FWHM, Δλ) and lifetimes (τ_m).     

Emission analysis of Dy and Pr:Bi2O3-ZnF2-B2O3-Li2O-Na2O glasses

In this paper, we present the spectral results of Dy³⁺ and Pr³⁺ (1.0 mol%) ions doped Bi₂O₃-ZnF₂-B₂O₃-Li₂O-Na₂O glasses. Measurements of X-ray diffraction (XRD), differential scanning calorimetry (DSC) profiles of these rare-earth ions doped glasses have been carried out. From the DSC thermograms, glass transition (T_g), crystallization (T_c) and melting (T_m) temperatures have been evaluated. The direct and indirect optical band gaps have been calculated based on the glasses UV absorption spectra. The emission spectrum of Dy³⁺:glass has shown two emission transitions ⁴F_7/2→⁶H_15/2 (482 nm) and ⁴F_7/2→⁶H_13/2 (576 nm) with an excitation at 390 nm wavelength and Pr³⁺:glass has shown a strong emission transition ¹D₂→³H₄ (610 nm) with an excitation at 445 nm. Upon exposure to UV radiation, Dy³⁺ and Pr³⁺ glasses have shown bright yellow and reddish colors, respectively, from their surfaces.