Luminescent materials consisting of Eu(III) ions complexed in heteropolyoxometalates incorporated into silica xerogels

Luminescent materials based on the energy transfer effect consist of heteropolyoxometalates of the type K₁₃[Eu(SiMo_xW_11−xO₃₉)₂] incorporated into xerogel matrices. Results of our experiments suggest that not only the composition parameter x (where x = 1, 3 and 5) of the salts with Eu(III) complex but also the type of the matrix influence the luminescent properties of these materials. The luminescent samples were characterized by such luminescence parameters as emission intensity, luminescence lifetime and quantum yield. The highest emission intensity of Eu(III) ions was exhibited by the salt with x = 1 incorporated into a silicate modified with 3-glycidoxypropyl groups. The longest lifetime was found in the material with a methylated silicate matrix with the same salt. For the complexed Eu(III) ions in these materials there is a correlation between emission intensity changes of the ⁵D₀ → ⁷F₂ band and the quantum yield. The materials with a high organic content in matrices such as the silicates with 3-glycidoxypropyl groups (either with closed or opened epoxy cycles) are more thermally unstable and they undergo larger photochemical degradation during exposure on UV radiation than the systems with limited organic content.     

Energy transfer and surface plasmon resonance in luminescent materials based on Tb(III) and Ag or Au nanoparticles in silica xerogel

Two-component material consisting of terbium(III) ions doping silica xerogel prepared by sol–gel procedure shows enhanced Tb(III) photoluminescence. We postulate that in this material the enhancement is owing to energy transfer from one of the defect states in silica to emitting states ³D₃ and ⁵D₄ of Tb(III).Surface plasmon resonance effect causes two contrary phenomena. Thus, if in the vicinity of the Tb(III) emission centers are present nanoparticles of Ag, observed is additional improvement of the Tb(III) emission. While, presence of Au nanostructures in the silica doped with Tb(III) causes quenching of the luminescence. In general, both the three-component materials exhibit enhancement of the component silica emission band in the resultant 380 nm band and relatively high thermal stability, especially above 600 °C.     

Luminescence properties and energy transfer of Eu/Tb ions codoped aluminoborosilicate glasses

Eu/Tb codoped aluminoborosilicate glasses were fabricated by high temperature melting-quenched technique and their luminescence properties were investigated by excitation and emission spectra. Under 376 nm excitation, blue, green and red emission bands were simultaneously observed at 425 nm, 485 nm, 540 nm and 611 nm, respectively. The broad blue emission band centered at 425 nm was originated from the reduced Eu²⁺ ions, which were reduced from Eu³⁺ ions at high temperature in an ambient atmosphere and the reduction process may be related with the optical basicity of glass matrix. A complex bright white light emission was obtained for 0.5 mol% Eu₂O₃, 0.5 mol% Tb₂O₃ codoped aluminoborosilicate glass with CIE-X = 0.31 and CIE-Y = 0.33. The energy transfer among Eu³⁺, Eu²⁺ and Tb³⁺ ions was also discussed.     

Tb3+-impregnated,non-porous silica glass possessing intense green luminescence under UV and VUV excitation

A colorless transparent luminescence material was successfully prepared by impregnation of leached, porous glass with Tb³⁺ ions followed by reductive sintering in a CO atmosphere. Tb³⁺ emissions under ultraviolet (UV) and vacuum ultraviolet (VUV) excitation clearly showed the most intense emission band to be situated at 543 nm, which corresponds to the ⁵D₄ → ⁷F₅ transition. Sintering of the Tb glass in a reducing atmosphere resulted in a significant enhancement of Tb³⁺ emission intensity in comparison with sintering in air. The presence of traces of cerium ions was verified in Tb glasses, and more Ce³⁺ ions were produced as a result of the reductive sintering. The increase in Ce³⁺ ions was believed to be mainly responsible for the enhancement of ⁵D₃ → ⁷F_j and ⁵D₄ → ⁷F_j transitions from Tb³⁺ ions owing to an energy transfer channel. A clearly defined difference in the spectral energy distribution of Tb³⁺ emissions was found for 231 nm UV and 160 nm VUV excitation of the Tb glass. The phenomenon of cross relaxation was only observed under 231 nm UV excitation. Different excitation mechanisms were taken into account. Direct excitation of Tb³⁺ ions together with Ce³⁺ ions occurred in the Tb glass under the 231 nm UV light, whereas indirect excitation consisting of host absorption of energy and transfer from host to Tb³⁺ ions occurred under the 160 nm VUV light.     

Comparative study on photoluminescence of amorphous and nano-crystalline YAG:Tb phosphors prepared by a combustion method

Amorphous and nano-crystalline Y₃Al₅O₁₂:Tb phosphor samples were obtained via a facile combustion method by calcination at various temperatures, using yttrium oxide and aluminum nitrite as starting materials and citric acid as fuel. XRD, FT-IR and TEM results showed that the products were amorphous if prepared at 750 °C, well-crystalline when treated above 850 °C. In addition, partially crystalline YAG phase was observed at 800 °C (in air). The excitation spectra of the samples calcined at 750 °C and 800 °C exhibited some difference in the 230–255 nm range in comparison to those of nano-crystalline YAG:Tb, i.e. an extra band centered at 250 nm was detected via Gaussian curve-fitting. Furthermore, the photoluminescence intensity of as-synthesized samples decreased obviously with increasing the crystallinity under 250 nm excitation. Contrary, it increased monotonously when altering the excitation wavelength to 323 nm. The concentration-dependent emission spectra of samples calcined at 800 °C revealed that the strongest intensity could be obtained with 10% Tb doping. Red-shifts indicated changes of the inter-atomic distances within the Tb³⁺ coordination polyhedron with increasing Tb concentration. The low temperature photoluminescence of partially crystalline YAG:10% Tb was also investigated, displaying good-resolution but reduced intensity compared to the room-temperature photoluminescence.     

Characterization,luminescence and EPR investigations of Eu2+ activated strontium aluminate phosphor

Strong blue-green light emitting Eu doped SrAl₂O₄ phosphor was synthesized by a low-temperature initiated, self-propagating and gas producing combustion process in a very short time (<5 min). The prepared powder was characterized by X-ray diffraction, Fourier-transform infrared spectrometry and scanning electron microscopy. The excitation spectrum shows a peak at 397 nm. Upon excitation at 397 nm, the emission spectrum exhibits a well defined broad band with maximum at 493 nm corresponding to 4f⁶5d → 4f⁷ transition. Electron paramagnetic resonance (EPR) measurements at X-band showed low field signals due to Eu²⁺ ions in SrAl₂O₄:Eu.     

Textural and adsorption characteristics of carbon xerogel adsorbents for removal of Cu (II) ions from aqueous solution

Resorcinol–formaldehyde (RF) carbon xerogels were synthesized using different resorcinol/sodium carbonate catalyst molar ratios (R/C = 50, 200, 500 and 1000) and heat treatment temperatures (HTT = 500, 600 and 700) under no external gas flow. The carbon adsorbents were extensively characterized by CHO content, FTIR, TEM and nitrogen adsorption isotherm at 77 K. The effect of R/C, HTT and oxygen content on the development of porosity within carbons was studied. Also, the adsorption capacity of these adsorbents was investigated by the removal of copper (II) ions from aqueous solution using single bottle test. The produced carbon xerogels exhibit a micro-mesopore character, but with different extents depending on the mechanism of porosity generation in relation to R/C, HTT and oxygen functional groups. Results show that the optimum conditions to obtain porous carbon xerogels were the highest R/C = 500–1000 in combination with carbonization preferably at 600 or 700 °C. Single bottle removal of Cu (II) ions indicated the developed carbons with appreciable capacity (q_u = 32–130 mg/g) which are controlled by the surface area and surface chemical nature (acidic O-functional groups). Finally, the present investigation provides a new, nanoporous type of porous carbon adsorbents with high adsorption capacity for removal of heavy metals from wastewater media.     

Nonlinear optical properties of PbS quantum dots in boro-silicate glass

PbS quantum dots synthesis in boro-silicate glass is presented. Absorption bleaching of PbS quantum dots of ≈4 and ≈7 nm in diameter dispersed in this glass has been studied. Bleaching relaxation time of 20–30 ps, absorption saturation fluence of ≈5 mJ/cm² and ground-state absorption cross-section of 2 ÷ 6 × 10⁻¹⁷ cm² at the wavelengths corresponding to the first excitonic absorption band maxima are measured.     

Time-resolved photoluminescence of implanted SiO2:Si+ films

In this paper we present results of a low-temperature time-resolved photoluminescence (PL) investigation of thin SiO₂ films implanted with silicon ions. In addition to the luminescence of well-known ODCs, some other bands are present in the low-energy region of PL spectra that are attributed to silicon nanoclusters (quantum dots – SiQDs), excitons and hydrogen-related species (HRS). Specific features of SiQD and HRS bands are the nanosecond kinetics and unusual “stepped” PL excitation spectrum in the 3.5–7.5 eV range. The possible origin of discovered phenomena is discussed. The obtained results are interpreted taking into account the interference of exciting radiation and dimensional quantization effects.     

Synthesis and luminescent properties of novel RENbO4:Ln3+ (RE = Y, Gd, Lu; Ln = Eu, Tb) micro-crystalline phosphors

Using rare earth coordination polymers with aromatic carboxylic acids as the precursors of rare earth oxide components, with polyethylene glycol (PEG) as the dispersing media, micro-crystalline phosphors RENbO₄:Ln³⁺ (RE = Y, Gd, Lu; Ln = Eu, Tb) have been synthesized by an in situ co-precipitation method. Both X-ray diffraction and scanning electron microscopy have shown that the resultant samples present are crystalline with ‘rice glue ball’ micro-morphology and crystalline grain sizes in the range of 1–2 μm. The luminescent properties of these phosphors have been studied, which show that the best photoluminescent performance is achieved for GdNbO₄:Tb³⁺ or Eu³⁺. This was because Gd³⁺ plays an important role to enhance the luminescence of Tb³⁺ or Eu³⁺ in an energy transfer process. In addition, the influence of the doping concentration on the fluorescence behaviors has been examined. With increase of the doping concentration from 1 mol% to 5 mol%, both the red emission intensity of Eu³⁺ and the green emission intensity of Tb³⁺ increase.     

Photoluminescence of undoped and B-doped ZnO in silicate glasses

Photoluminescence of undoped and B-doped ZnO in silicate glasses was investigated by varying the concentration of ZnO (35–50 mol%) and B dopant (0–10 mol%) in the glass matrices. The broad and intense near band edge emissions were observed while the visible light emission was very weak. UV luminescence in all samples was red-shifted relative to the exciton transition in bulk ZnO and enhanced by decreased ZnO concentration due to higher degree of structural integrity and the lower aggregation degree of ZnO. Donor B dopant played the double roles of filling conduction bands to broaden band gap when its concentration was lower than 5 mol%, and emerging with conduction bands to narrow the gap when B dopant exceeded this value.     

Novel polymer–inorganic hybrid materials fabricated with in situ composition and luminescent properties

A new polymer–inorganic material was synthesized from terephthalic acid (TPA) and rare-earth ion (Tb³⁺, Eu³⁺) complex, which rare-earth ions connect with polymer by covalent bands. The luminescent europium and terbium coordination polymers, PET–Tb and PET–Eu, were produced in situ through low temperature solution polycondensation (PET = polyethyl terephthate ester). FTIR spectroscopy, ultraviolet absorption and scanning electron microscopy were applied to characterize the structure of obtained hybrid material. Phosphorescence and fluorescence spectra were applied to characterize the photophysical properties of the obtained hybrid material. The experimental result shows that the strong luminescence of rare-earth ions substantiates optimum energy match and effective intramolecular energy transfer between the triplet state energy of coordination complex and the emissive energy level of the rare-earth ions. The hybrid material systems can be expected to have potential applications in photophysical sensors.     

Spectroscopy and crystal-field analysis of Cr4+-doped transparent silicate glass-ceramics

We report transparent Cr⁴⁺-doped SiO₂–Al₂O₃–ZnO–Li₂O–K₂O glass-ceramics with broadband infrared luminescence. After heart-treatment, Li₂ZnSiO₄ crystallite was precipitated in the glasses, and its average size increased with increasing heat-treatment temperature. Racah parameters of Cr⁴⁺–Li₂ZnSiO₄ glass-ceramics have been calculated, and it was confirmed from absorption spectra that the energy levels of Cr⁴⁺-doped glass-ceramics are close to the cross point ¹E and ³T states. No infrared emission was detected in the as-made glass samples, but the broadband infrared emission centered at 1210 nm with the full width at half maximum (FWHM) of more than 250 nm was observed by exciting the glass-ceramics with excitation of an 808 nm laser diode. In order to analyze the located crystal field of Cr⁴⁺ ions, the emission spectra are fitted by multi-peak Gauss fitting. It is seen that the fluorescence spectra are fitted into two Gaussian bands at around 1195 and 1263 nm with band widths of 208 and 278 nm, respectively. The two Gaussian bands at around 1195 and 1263 nm have about the same decay rate, and hence they would probably originate from the same luminescent centers. The observed infrared emission could be attributed to Cr⁴⁺ ions at low-field sites in Li₂ZnSiO₄ glass-ceramics.     

Photo and electroluminescence behavior of Tb(ACAC)3phen complex used as emissive layer on organic light emitting diodes

This work shows the luminescence properties of a rare-earth organic complex, the Tb(ACAC)₃phen. The results show the ⁵D₄ → ⁷F_3,4,5,6 transitions with no influence of the ligand. The photoluminescence excitation spectrum is tentatively interpreted by the ligands absorption. An organic light emitting diode (OLED) was made by thermal evaporation using TPD (N,N′-bis(3-methylphenyl)N,N′-diphenylbenzidine) and Alq3 (aluminum-tris(8-hydroxyquinoline)) as hole and electron transport layers, respectively. The emission reproduces the photoluminescence spectrum of the terbium complex at room temperature, with Commission Internationale de l’Éclairage – CIE (x, y) color coordinates of (0.28, 0.55). No presence of any bands from the ligands was observed. The potential use of this compound in efficient devices is discussed.     

The effects of ZnO coating on the photoluminescence properties of porous silicon for the advanced optoelectronic devices

In the present work we investigate, the role of zinc oxide (ZnO) thin films passivating layer deposited by rf magnetron sputtering at room temperature on low (18%) and high (80%) porosity porous silicon (PS). The micro-Raman spectroscopy, Fourier transform infrared spectroscopy (FTIR) and atomic force microscopy (AFM) analysis have been carried out to understand the effect of ZnO films coating on PS. A systematic investigation from Raman spectroscopy suggests the formation of a good quality ZnO wurtzite structure on PS. The photoluminescence (PL) measurements on PS and ZnO coated PS shows a red, blue and UV emission bands at around ～1.8, ～2.78 and ～3.2 eV. An enhancement of all PL emission bands have been achieved after ZnO films deposition on high porosity PS.     

Structural and spectroscopic characterization of poly(styrene sulfonate) films doped with neodymium ions

This work reports the structural and spectroscopy characterization of poly(styrene sulfonate) (PSS) films doped with neodymium (Nd) ions. Nd–PSS films were processed using the acid of poly(styrene sulfonate) – H–PSS and neodymium nitrate – Nd(NO₃)₃; the maximum incorporation of Nd ions in the polymeric matrix was equal 19.3%. The absorption in the UV–Vis–NIR spectral region presents typical electronic transitions of Nd³⁺ ions, with well resolved peaks. The infrared spectra present the transition bands of PSS with characteristic line shape broadening, and the presence of vibrational modes of N–O groups in the range of 1400–720 cm^?1, prove the permanence of Nd(NO₃)_x, with x = 1, 2 and/or 3, in the H–PSS matrix. UV–Vis site selective photoluminescence data indicate that the incorporation of Nd³⁺ introduces a blue shift in PSS emission (325–800 nm), decreasing the interaction between adjacent PSS lateral groups (aromatic rings). Nd³⁺ reabsorption and energy transfer effects between the PSS matrix and Nd³⁺ were also observed. The IR emission of Nd–PSS films at 1076 nm (⁴F_3/2 → ⁴I_11/2) present constant efficiency, independent on Nd³⁺ concentration. The Judd–Ofelt theory was employed to analyze radiative properties. The excitation spectra prove the energy transfer between the polymeric matrix and Nd³⁺. Complex impedance data was used to probe relaxation processes during the charge transport within the polymeric matrix.     

Lead sulfide quantum dots in glasses controlled by silver diffusion

Precipitation of PbS quantum dots (QDs) in silicate glasses controlled by Ag⁺ ion diffusion was investigated. Ag⁺ ions penetrated ~ 0.5 μm into the glass when the glass was immersed in the AgNO₃ solution at 80 °C. Ag nano-particles (NPs) and PbS QDs were formed after heat-treatment at temperatures of 420–460 °C for 10 h. PbS QDs in Ag⁺-diffused regions photoluminesced at longer wavelengths than did those in Ag⁺-free regions. This indicates that PbS QDs thus formed in regions containing Ag NPs were larger than those in Ag⁺-free regions and this size difference was confirmed from the transmission electron microscope images. PbS QDs can grow at temperature as low as 420 °C in Ag⁺-diffused regions and this implies that PbS QDs form preferentially using Ag NPs as nucleating agents.     

Construction and photoluminescence of amorphous silicone resins containing lanthanide ions as luminescent center

Three series of luminescent silicone resins have been synthesized. This ternary resin (SiPy-La-L, La = Eu, Tb or Dy; L = 1, 10-phenanthroline or acetylacetone) is composed from the precursor, the second ligand and lanthanide ions using a sol–gel method. The precursor is derived from the hydrosilylation reaction of methyldichlorsilane and 4-vinylpyrodine. Lanthanide ions (Eu³⁺, Tb³⁺ and Dy³⁺) act as luminescent center. Structure and texture of silicone resins are characterized by the X-ray diffraction (XRD) and scanning electron microscopy (SEM). The luminescence of silicone resins are monitored and studied in detail. Red and green luminescences are checked when silicone resins are exposed to ultraviolet light, suggesting that the intra-molecular energy-transfer processes take place within these silicone resins.     

Synthesis,characterization and photoluminescence of ZnO spindles by polyvinylpyrrolidone-assisted low-temperature wet-chemistry process

ZnO spindles were prepared by wet-chemistry process with surfactant polyvinylpyrrolidone at a low temperature of 35 °C. The morphologies and structures of the products were characterized by X-ray powder diffraction, field emission scanning electron microscopy, and high-resolution transmission electron microscopy. The addition of polyvinylpyrrolidone promoted the formation of ZnO crystal nuclei, and accelerated the growth rate of (0001) plane rich in Zn²⁺ ions. The as-obtained ZnO spindles were twin crystal wurtzite structures, with the size of 30 nm at the tips, 350–450 nm at the center, and 1–1.5 μm in length. The room-temperature photoluminescence results showed that surface effects played a major role in the luminescence of the ZnO spindles, which exhibited a broad violet–blue–green emission band related to deep level defects. We proposed a new growth mechanism, which might be useful for applications in synthesis of size- and shape-controlled ZnO crystals.     

Photoluminescence of Si nanocrystallites in different types of matrices

This paper presents the comparative investigation of photoluminescence (PL) and its temperature dependence for rf-magnetron co-sputtered Si-enriched SiO_x systems and amorphous Si films prepared by hot-wire CVD method with Si nanocrystallites of different sizes. It is shown that PL spectra of Si–SiO_x films consist of the five PL bands peaked at 1.30, 1.50, 1.76, 2.05 and 2.32 eV. Amorphous Si films with Si nanocrystallites are characterized by three PL bands only peaked at 1.35, 1.50 and 1.76 eV. The peak position of the 1.50 eV PL band shifts with the change of Si quantum dot sizes and it is attributed to exciton recombination inside of Si quantum dots. The nature of four other PL bands is discussed as well.