The effect of high-temperature annealing on optical properties of porous anodic alumina formed in oxalic acid.

Photoluminescence (PL) of anodic alumina membranes (AAMs) with ordered nanopore arrays fabricated in oxalic acid has been investigated under different annealing temperatures. X-ray diffraction reveals the structural transition from the amorphous state to crystallization. PL measurements show that a blue PL band occurs in the wavelength range 300-600 nm. The differential thermal analysis (DTA) and thermogravimetric analysis (TG) results revealed plentiful oxalic ions incorporated into the prepared AAMs. The PL band of AAMs could be attributed to the co-actions of the oxygen vacancies (F(+) and F centres) and the luminescent centres transformed from oxalic impurities. With the increase of the annealing temperature, the intensities of PL increase first, and at 500 degrees C reach a maximum value, then decrease. The PL phenomenon is intimately related to the temperature-induced structural transitions. There are three optical centres in the annealed AAMs; the first is originates from the F centres, the second is correlated with F(+) centres and the third is associated with the oxalic impurities incorporated in the AAMs.     

Effect of capping agent on the particle size of CdSe nanoparticles

CdSe nanoparticles were synthesized by green route and chemical route methods. In the green route method the samples were capped by starch and in the chemical route method the samples were capped by mercaptoacetic acid (MAA). The samples were characterized by powder X‐ ray diffraction (XRD) and transmission electron microscopy (TEM). Both the samples showed zinc blend structure. The optical absorption spectra and Fourier transform infrared (FTIR) spectra were also studied. A blue shift was seen in the absorption spectra as compared with the bulk as well as the sample capped by starch. TEM images showed agglomeration for the starch‐capped sample as compared with the MAA‐capped sample. The particle size for the sample capped by MAA was found to be less as compared with the starch‐capped sample. A blue shift in the photoluminescence (PL) spectra was also recorded for the samples prepared by the chemical route as compared with the sample prepared by the green route as well as the bulk. The PL peak shifted towards the red side and increase in the peak intensity occurred with the change in the excitation wavelength. Change in PL intensity was observed with different pH at 685 nm. Copyright © 2016 John Wiley & Sons, Ltd.     

Photoluminescence,cathodoluminescence and thermal stability of Sm3+‐activated Sr3La(VO4)3 red‐emitting phosphors

A series of Sm³⁺‐activated Sr₃La(VO₄)₃ phosphors were synthesized by a facile sol‐gel method. X‐ray diffraction patterns and photoluminescence (PL)/cathodoluminescence (CL) spectra as well as PL decay curves were employed to characterize the obtained samples. Upon 402 nm light excitation, the characteristic emissions of Sm³⁺ ions corresponding to ⁴G_5/2→⁶H_J transitions were observed in all the as‐prepared products. The PL emission intensity was increased with increase in Sm³⁺ ion concentration, while concentration quenching occurred when the doping concentration was over 4 mol%. The non‐radiative energy transfer mechanism for concentration quenching of Sm³⁺ ions was dominated by dipole–dipole interaction and the critical distance was around 21.59 Å. Furthermore, temperature‐dependent PL emission spectra revealed that the obtained phosphors possessed good thermal stability with an activation energy of 0.19 eV. In addition, the CL spectra of the samples were almost the same as the PL spectra, and the CL emission intensity showed a tendency to increase with increase in accelerating voltage and filament current. These results suggest that the Sm³⁺‐activated Sr₃La(VO₄)₃ phosphors with good color coordinates, high color purity and superior thermal stability may be a potential candidate for applications in white light‐emitting diodes and field‐emission displays as red‐emitting phosphors.     

Influence of thiol capping on the photoluminescence properties of L‐cysteine‐, mercaptoethanol‐ and mercaptopropionic acid‐capped ZnS nanoparticles

Mercaptoethanol (ME), mercaptopropionic acid (MPA) and L‐cysteine (L‐Cys) having ‐SH functional groups were used as surface passivating agents for the wet chemical synthesis of ZnS nanoparticles. The effect of the thiol group on the optical and photoluminescence (PL) properties of ZnS nanoparticles was studied. L‐Cysteine‐capped ZnS nanoparticles showed the highest PL intensity among the studied capping agents, with a PL emission peak at 455 nm. The PL intensity was found to be dependent on the concentration of Zn²⁺ and S^2– precursors. The effect of buffer on the PL intensity of L‐Cys‐capped ZnS nanoparticles was also studied. UV/Vis spectra showed blue shifting of the absorption edge. Copyright © 2015 John Wiley & Sons, Ltd.     

Effect of annealing on down‐conversion properties of monoclinic Gd2O3:Er3+ nanophosphors

Erbium‐doped nano‐sized Gd₂O₃ phosphor was prepared by a solution combustion method in the presence of urea as a fuel. The phosphor was characterized by X‐ray diffractometry (XRD), Fourier transform infra‐red spectroscopy, energy dispersive X‐ray analysis (EDX) and transmission electron microscopy (TEM). The results of the XRD shows that the phosphor has a monoclinic phase, which was further confirmed by the TEM results. Particle size was calculated by the Debye–Scherrer formula. The erbium‐doped Gd₂O₃ nanophosphor was revealed to have good down‐conversion (DC) properties and the intensity of phosphor could be modified by annealing. The effects of annealing at 900°C on the particle size and luminescence properties were studied and compared with freshly prepared Gd₂O₃:Er³⁺ nanoparticles. The average particle sizes were calculated as 8 and 20 nm for the freshly prepared samples and samples annealed at 900°C for 1 h, respectively. The results show that both freshly prepared and annealed Gd₂O₃:Er³⁺ have monoclinic structure. Copyright © 2014 John Wiley & Sons, Ltd.     

γ-irradiation of PEGd,lPLA and PEG-PLGA Multiblock Copolymers: II. Effect of Oxygen and EPR Investigation

The purpose of this research was to evaluate how the presence of oxygen can affect irradiation-induced degradation reactions of PEGd,lPLA and PEG-PLGA multiblock copolymers submitted to gamma irradiation and to investigate the radiolytic behavior of the polymers. PEGd,lPLA, PEG-PLGA, PLA, and PLGA were irradiated by using a ⁶⁰Co irradiation source in air and under vacuum at 25 kGy total dose. Mw and Mn were evaluated by gel permeation chromatography. The stability study was carried out on three samples sets: (a) polymer samples irradiated and stored in air, (b) polymer samples irradiated and stored under vacuum, and (c) polymer samples irradiated under vacuum and stored in air. The thermal and radiolytic behavior was investigated by differential scanning calorimetry and electron paramagnetic resonance (EPR), respectively. Samples irradiated in air showed remarkable Mw and Mn reduction and Tg value reduction due to radiation-induced chain scission reactions. Higher stability was observed for samples irradiated and stored under vacuum. EPR spectra showed that the presence of PEG units in multiblock copolymer chains leads to: (a) decrease of the radiolytic yield of radicals and (b) decrease of the radical trapping efficiency and faster radical decay rates. It can be concluded that the presence of oxygen during the irradiation process and the storage phase significantly increases the entity of irradiation-induced damage.     

Investigation on the pH‐independent photoluminescence emission from carbon dots impregnated on polymer matrix

Highly luminescent, polymer nanocomposite films based on poly(vinyl alcohol) (PVA), and monodispersed carbon dots (C‐dots) derived from multiwalled carbon nanotubes (MWCNTs), as coatings on substrates as well as free standing ones are obtained via solution‐based techniques. The synthesized films exhibit pH‐independent photoluminescence (PL) emission, which is an advantageous property compared with the pH‐dependent photoluminescence intensity variations, generally observed for the C‐dots dispersed in aqueous solution. The synthesized C‐dots and the nanocomposite films are characterized by transmission electron microscopy (TEM), scanning electron microscopy (SEM), X‐ray diffraction (XRD), Fourier transform infra‐red spectroscopy ( FTIR), ultraviolet (UV) ? visible spectroscopy and photoluminescence spectroscopy (PL) techniques. The TEM image provides clear evidence for the formation of C‐dots of almost uniform shape and average size of about 8 nm, homogeneously dispersed in aqueous medium. The strong anchoring of C‐dots within the polymer matrix can be confirmed from the XRD results. The FTIR spectral studies conclusively establish the presence of oxygen functional groups on the surfaces of the C‐dots. The photoluminescence (PL) emission spectra of the nanocomposite films are broad, covering most part of the visible region. The PL spectra do not show any luminescence intensity variations, when the pH of the medium is changed from 1 to 11. The pH‐independent luminescence, shown by these films offers ample scope for using them as coatings for designing diagnostic and imaging tools in bio medical applications. The non‐toxic nature of these nanocomposite films has been established on the basis of cytotoxicity studies.     

The size effect to O2−–Ce4+ charge transfer emission and band gap structure of Sr2CeO4

Sr₂CeO₄ phosphors with different crystalline sizes were synthesized by the sol–gel method or the solid‐state reaction. Their crystalline size, luminescence intensity of O^2??Ce⁴⁺ charge transfer and energy gaps were obtained through the characterization by X‐ray diffraction, photoluminescence spectra, as well as UV–visible diffuse reflectance measurements. An inverse relationship between photoluminescence (PL) spectra and crystalline size was observed when the heating temperature was from 1000°C to 1300°C. In addition, band energy calculated for all samples showed that a reaction temperature of 1200°C for the solid‐state method and 1100°C for sol–gel method gave the largest values, which corresponded with the smallest crystalline size. Correlation between PL intensity and crystalline size showed an inverse relationship. Band structure, density of states and partial density of states of the crystal were calculated to analyze the mechanism using the cambrige sequential total energy package (CASTEP) module integrated with Materials Studio software.     

Enhanced Stability of Perovskite Solar Cells Incorporating Dopant‐Free Crystalline Spiro‐OMeTAD Layers by Vacuum Sublimation

The main handicap still hindering the eventual exploitation of organometal halide perovskite‐based solar cells is their poor stability under prolonged illumination, ambient conditions, and increased temperatures. This article shows for the first time the vacuum processing of the most widely used solid‐state hole conductor (SSHC), i.e., the Spiro‐OMeTAD [2,2′,7,7′‐tetrakis (N,N‐di‐p‐methoxyphenyl‐amine) 9,9′‐spirobifluorene], and how its dopant‐free crystalline formation unprecedently improves perovskite solar cell (PSC) stability under continuous illumination by about two orders of magnitude with respect to the solution‐processed reference and after annealing in air up to 200 °C. It is demonstrated that the control over the temperature of the samples during the vacuum deposition enhances the crystallinity of the SSHC, obtaining a preferential orientation along the π–π stacking direction. These results may represent a milestone toward the full vacuum processing of hybrid organic halide PSCs as well as light‐emitting diodes, with promising impacts on the development of durable devices. The microstructure, purity, and crystallinity of the vacuum sublimated Spiro‐OMeTAD layers are fully elucidated by applying an unparalleled set of complementary characterization techniques, including scanning electron microscopy, X‐ray diffraction, grazing‐incidence small‐angle X‐ray scattering and grazing‐incidence wide‐angle X‐ray scattering, X‐ray photoelectron spectroscopy, and Rutherford backscattering spectroscopy.     

Sensitization enhancement of europium in ZnSe/ZnS core/shell quantum dots induced by efficient energy transfer

Eu‐doped ZnSe:/ZnS quantum dots (formed as ZnSe:Eu/ZnS QDs) were successfully synthesized by a two‐step wet chemical method: nucleation doping and epitaxial shell growing. The sensitization characteristics of Eu‐doped ZnSe and ZnSe/ZnS core/shell QD are studied in detail using photoluminescence (PL), PL excitation spectra (PLE) and time‐resolved PL spectroscopy. The emission intensity of Eu ions is enhanced and that of ZnSe QDs is decreased, implying that energy was transferred from the excited ZnSe host materials (the donor) to the doped Eu ions (the acceptor). PLE reveals that the ZnSe QDs act as an antenna for the sensitization of Eu ions through an energy transfer process. The dynamics of ZnSe:Eu/ZnS core/shell quantum dots with different shell thicknesses and doping concentrations are studied via PL spectra and fluorescence lifetime spectra. The maximum phosphorescence efficiency is obtained when the doping concentration of Eu is approximately 6% and the sample showed strong white light under ultraviolet lamp illumination. By surface modification with ZnS shell layer, the intensity of Eu‐related PL emission is increased approximately three times compared with that of pure ZnSe:Eu QDs. The emission intensity and wavelength of ZnSe:Eu/ZnS core/shell quantum dots can be modulated by different shell thickness and doping concentration. The results provide a valuable insight into the doping control for practical applications in laser, light‐emitting diodes and in the field of biotechnology. Copyright © 2014 John Wiley & Sons, Ltd.     

Synthesis and characterization of pure and Li+ activated Alq3 complexes for green and blue organic light emitting diodes and display devices

Pure and Li⁺‐doped Alq₃ complexes were synthesized by simple precipitation method at room temperature, maintaining the stoichiometric ratio. These complexes were characterized by X‐ray diffraction, ultraviolet‐visible absorption and Fourier transform infrared and photoluminescence (PL) spectra. X‐ray diffraction analysis reveals the crystalline nature of the synthesized complexes, while Fourier transform infrared spectroscopy confirm the molecular structure, the completion of quinoline ring formation and presence of quinoline structure in the metal complex. Ultraviolet‐visible and PL spectra revealed that Li⁺ activated Alq₃ complexes exhibit the highest intensity in comparison to pure Alq₃ phosphor. Thus, Li⁺ enhances PL emission intensity when doped into Alq₃ phosphor. The excitation spectra lie in the range of 383–456 nm. All the synthesized complexes other than Liq give green emission, while Liq gives blue emission with enhanced intensity. Thus, he synthesized phosphors are the best suitable candidates for green‐ and blue‐emitting organic light emitting diode, PL liquid‐crystal display and solid‐state lighting applications. Copyright © 2013 John Wiley & Sons, Ltd.     

Ca2Al2SiO7:Ce3+ phosphors for mechanoluminescence dosimetry

A series of Ce³⁺ ion single‐doped Ca₂Al₂SiO₇ phosphors was synthesized by a combustion‐assisted method at an initiating temperature of 600 °C. The samples were annealed at 1100 °C for 3 h and their X‐ray diffraction patterns confirmed a tetragonal structure. The phase structure, particle size, surface morphology and elemental analysis were analyzed using X‐ray diffraction (XRD), transmission electron microscope (TEM), scanning electron microscopy (SEM) and energy dispersive X‐ray (EDX) spectroscopy techniques. Thermoluminescence (TL) intensity increased with increase in ultraviolet (UV) light exposure time up to 15 min. With further increase in the UV irradiation time the TL intensity decreases. The increase in TL intensity indicates that trap concentration increased with UV exposure time. A broad peak at 121 °C suggested the existence of a trapping level. The peak of mechanoluminescence (ML) intensity versus time curve increased linearly with increasing impact velocity of the moving piston. Mechanoluminescence intensity increased with increase in UV irradiation time up to 15 min. Under UV‐irradiation excitation, the TL and ML emission spectra of Ca₂Al₂SiO₇:Ce³⁺ phosphor showed the characteristic emission of Ce³⁺ peaking at 400 nm (UV–violet) and originating from the Ce³⁺ transitions of 5d‐4f (²F_5/2 and ²F_7/2). The photoluminescence (PL) emission spectra for Ca₂Al₂SiO₇:Ce³⁺ were similar to the ML/TL emission spectra. The mechanism of ML excitation and the suitability of the Ca₂Al₂SiO₇:Ce³⁺phosphor for radiation dosimetry are discussed. Copyright © 2016 John Wiley & Sons, Ltd.     

Rapid,controllable, one‐pot and room‐temperature aqueous synthesis of ZnO:Cu nanoparticles by pulsed UV laser and its application for photocatalytic degradation of methyl orange

Zinc oxide (ZnO) and ZnO:Cu nanoparticles (NPs) were synthesized using a rapid, controllable, one‐pot and room‐temperature pulsed UV‐laser assisted method. UV‐laser irradiation was used as an effective energy source in order to gain better control over the NPs size and morphology in aqueous media. Parameters effective in laser assisted synthesis of NPs such as irradiation time and laser shot repetition rate were optimized. Photoluminescence (PL) spectra of ZnO NPs showed a broad emission with two trap state peaks located at 442 and 485 nm related to electronic transition from zinc interstitial level (I_Zn) to zinc vacancy level (V_Zn) and electronic transition from conduction band to the oxygen vacancy level (V_O), respectively. For ZnO:Cu NPs, trap state emissions disappeared completely and a copper (Cu)‐related emission appeared. PL intensity of Cu‐related emission increased with the increase in concentration of Cu²⁺, so that for molar ratio of Cu:Zn 2%, optimal value of PL intensity was obtained. The photocatalytic activity of Cu‐doped ZnO revealed 50 and 100% increasement than that of undoped NPs under UV and visible irradiation, respectively. The enhanced photocatalytic activity could be attributed to smaller crystal size, as well as creation of impurity acceptor levels (T₂) inside the ZnO energy band gap.     

Enhancing the luminescence of Eu3+/Eu2+ ion‐doped hydroxyapatite by fluoridation and thermal annealing

This paper reports a novel way for the synthesis of a europium (Eu)‐doped fluor‐hydroxyapatite (FHA) nanostructure to control the luminescence of hydroxyapatite nanophosphor, particularly, by applying optimum fluorine concentrations, annealed temperatures and pH value. The Eu‐doped FHA was made using the co‐precipitation method followed by thermal annealing in air and reducing in a H₂ atmosphere to control the visible light emission center of the nanophosphors. The intensities of the OH^? group decreased with the increasing fluorine concentrations. For the specimens annealed in air, the light emission center of the nanophosphor was 615 nm, which was emission from the Eu³⁺ ion. However, when they were annealed in reduced gas (Ar + 5% H₂), a 448 nm light emission center from the Eu²⁺ ion of FHA was observed. The presence of fluorine in Eu‐doped FHA resulted in a significant enhancement of nanophosphor luminescence, which has potential application in light emission and nanomedicine.     

Effect of thermal annealing on the structural and optical properties of tris‐(8‐hydroxyquinoline)aluminum(III) (Alq3) films

Tris‐(8‐hydroxyquionoline)aluminum (Alq₃) was synthesized and coated on to a glass substrate using the dip coating method. The structural and optical properties of the Alq₃ film after thermal annealing from 50°C to 300°C in 50° steps was studied. The films have been prepared with 2 to 16 layers (42–324 nm). The thickness and thermal annealing of Alq₃ films were optimized for maximum luminescence yield. The Fourier transform infrared spectrum confirms the formation of quinoline with absorption in the region 700 ? 500/cm. Partial sublimation and decomposition of quinoline ion was observed with the Alq₃ films annealed at 300°C. The X‐ray diffraction pattern of the Alq₃ film annealed at 50°C to 150°C reveals the amorphous nature of the films. The Alq₃ film annealed above 150°C were crystalline nature. Film annealed at 150°C exhibits a photoluminescence intensity maximum at 512 nm when excited at 390 nm. The Alq₃ thin film deposited with 10 layers (220 nm) at 150°C exhibited maximum luminescence yield. Copyright © 2014 John Wiley & Sons, Ltd.     

Enhanced chemiluminescence of the luminol–AgNO3 system by Ag nanoparticles

The oxidation reaction of luminol with AgNO₃ can produce chemiluminescence (CL) in the presence of silver nanoparticles (NPs) in alkaline solution. Based on the studies of UV‐vis absorption spectra, photoluminescence (PL) spectra and CL spectra, a CL enhancement mechanism is proposed. The CL emission spectrum of the luminol–AgNO₃–Ag NPs system indicated that the luminophore was still 3‐aminophthalate. On injection of silver nanoparticles into the mixture of luminol and AgNO₃, they catalysed the reduction of AgNO₃ by luminol. The product luminol radicals reacted with the dissolved oxygen, to produce a strong CL emission. As a result, the CL intensity was substantially increased. Moreover, the influences of 18 amino acids, e.g. cystine, tyrosine and asparagine, and 25 organic compounds, including gallic acid, tannic acid and hydroquinone, on the luminol–AgNO₃–Ag NPs CL system were studied by a flow‐injection procedure, which led to an effective method for detecting these compounds. Copyright © 2011 John Wiley & Sons, Ltd.     

Thermoluminescence properties of annealed natural quartz after beta irradiation

Here we investigated the effects of annealing, heating rate and fading (after annealing at 800 °C) on the thermoluminescence (TL) glow curves of natural quartz (NQ). All of the samples were annealed at different temperatures between 100 °C and 800 °C and then irradiated with a beta dose of about 34 Gray (Gy), in order to determine the effects of annealing treatments on TL peaks of natural quartz. TL glow curves of the samples were recorded. It was observed that the intensities of TL peaks were strongly sensitive to annealing temperatures at 800 °C. The heating rate and fading effect of TL peaks of natural quartz were examined for the annealed samples at 800 °C for 30 min. It was observed that the intensities of the TL peaks were differently affected from heating rate and fading. Additionally, TL kinetic parameters (activation energy, frequency factor and order of kinetics) of all peaks were determined for annealed samples using a computerized glow curve deconvolution (CGCD) method and Mathematica software. Copyright © 2016 John Wiley & Sons, Ltd.     

Luminescence study of monodispersed ZnS nanoparticles

Monodispersed ZnS nanoparticles have been successfully synthesized by a chemical precipitation method in an air atmosphere using polyvinylpyrrolidone (PVP) and sodium hexametaphosphate (SHMP) as surfactants. The synthesized nanoparticles were characterized by X‐ray diffraction (XRD), transmission electron microscopy (TEM), Fourier transform infrared spectrometer (FT‐IR), UV–Vis optical absorption and photoluminescence (PL) spectra. Prepared surfactants capped ZnS nanoparticles are highly homogeneous and well dispersed. Optical absorption spectra showed a strong blue shift from the uncapped particles due to the quantum confinement effect. The capped ZnS emission intensity is enhanced than more the uncapped particles. The size of the synthesized particles is around 4–6.5 nm range. Copyright © 2012 John Wiley & Sons, Ltd.     

Luminescent properties of a novel fluorene organic material

The photo‐physical properties of 6,6′‐(9H‐fluoren‐9,9‐diyl)bis(2,3‐bis(9,9‐dihexyl‐9H‐fluoren‐2‐yl)quinoxaline) (BFLBBFLYQ) and its blend doped with N′‐biphenyl‐N,N′‐bis‐(3‐methylphenyl)‐1,1′‐biphenyl‐4,4′‐diamine (TPD) were investigated. The absorption, photoluminescence (PL) and electroluminescence (EL) properties of pristine BFLBBFLYQ and blend in solution and spin‐coated film are outlined, including a discussion of charge‐transfer (CT) exciplex emission of BFLBBFLYQ:TPD blend in the solid state. The luminescent properties of BFLBBFLYQ films using different deposition processes were studied. It was found that the low‐energy emission bands at 530–570 nm appeared in the PL spectra of BFLBBFLYQ evaporated films in ultra‐high vacuum. Also, the low‐energy band was the exclusive emission in the EL spectra of BFLBBFLYQ films. Copyright © 2008 John Wiley & Sons, Ltd.