Photoluminescence of spark-processed metals

The photoluminescence (PL) properties of spark-processed (sp) metals were systematically investigated. It was found that spark-processing of Cr, Cu, Fe, Mg, and Mn essentially yielded no PL at room temperature in the visible spectral range. In contrast, sp-Ti, Ta, Al, Ni, Mo, and Zn showed strong PL, which is in many respects comparable to sp-Si. It was further found that the PL intensity of the sp metals depends exponentially on the nitrogen concentration, which is contained in the spark-processing ambient (along with oxygen). This behavior was also found for sp-Si. In contrast, the PL intensities for native oxides (containing essentially no nitrogen) is several orders of magnitude smaller than those for sp-metals and the respective PL peaks are situated at higher energies. The results are discussed in the light of the self-trapped exciton model.     

Variation of spark-processing parameters on the photoluminescence properties of spark-processed silicon

Electrical and physical parameters, which influence the photoluminescence (PL) properties of spark-processed silicon (sp-Si), were systematically varied in order to obtain optimal PL emission. Among these parameters are the average spark current, the pulse width of the spark events, the frequency of the pulses, the processing time, the electrode diameter, the distance between the electrodes, the spark-processing environment, and the gas ambient pressure. It was found that for optimal PL emission the processing current needs to be between 20 and 40 mA, and the pulse frequency of the sparks between 10 and 15 kHz. Further, the N₂/O₂ ratio of the processing environment needs to be about 7:3 and the ambient gas pressure and the processing time as large as feasible. The conditions that are favorable for green PL are a small pulse width, a small counter electrode diameter, a small gap between electrodes, a relatively large nitrogen concentration in the processing chamber, and a comparatively large spark frequency. In the opposite cases, a UV/blue PL is predominantly observed. The results are discussed in terms of various thermal effects on the resulting molecules or defects, which are believed to be important for the PL emission.     

Photoluminescence of ZnO nanowires dependent on O2 and Ar annealing

High-purity ZnO nanowires have been synthesized on Si substrates without the presence of a catalyst at 600 °C by a simple thermal vapor technique. Photoluminescence (PL) spectra of the annealed samples at 900 °C under oxygen and argon gases have been investigated. After O₂ or Ar annealing, the PL visible-emission intensity that is related to intrinsic defects (oxygen vacancies) is greatly reduced compared with as-grown ZnO nanowires because the oxygen-gas ions or oxygen interstitials diffuse into the oxygen vacancies during annealing process. The blue-band peak of the O₂- or Ar-annealed ZnO naonowires is also smaller than the green-band peak in the visible broadband because of the reduction of oxygen vacancies. Therefore, the main intrinsic defects (oxygen vacancies) of as-grown ZnO nanowires can be reduced by O₂ or Ar annealing, which is an important procedure for the development of advanced optoelectronic ZnO nanowire devices.     

Simple chemical aqueous synthesis of dahlia nanoflower consisting of finger-like ZnO nanorods and observation of stable ultraviolet photoluminescence emission

In this work, we have reported the synthesis of dahlia flower-like ZnO nanostructures consisting of human finger-like nanorods by the hydrothermal method at 120 °C and without using any capping agent. Optical properties of the samples, including UV–vis absorption and photoluminescence (PL) emission characteristics are determined by dispersing the samples in water as well as in ethanol media. The quenching of PL emission intensity along-with the red shifting of the PL emission peak are observed when the samples are dispersed in water in comparison to those obtained after dispersing the samples in ethanol. It has been found that PL emission characteristic, particularly the spectral nature of PL emission, of the samples remains almost unaltered (except some improvement in UV PL emission) even after thermally annealing it for 2 h at the temperature of 300 °C. Also the synthesized powder samples, kept in a plastic container, showed a very stable PL emission even after 15 months of synthesis. Therefore, the synthesized samples might be useful for their applications in future optoelectronics devices.     

Synthesis and luminescence properties of YVO4:Eu,Bi phosphor with enhanced photoluminescence by Bi doping

YVO₄:Eu³⁺,Bi³⁺ phosphors have been prepared by the high-temperature solid-state (HT) method and the Pechini-type sol-gel (SG) method. Spherical SiO₂ particles have been further coated with YVO₄:Eu³⁺,Bi³⁺ phosphor layers by the Pechini-type SG process, and it leads to the formation of core-shell structured SiO₂/YVO₄:Eu³⁺,Bi³⁺ phosphors. Therefore, the phase formations, structures, morphologies, and photoluminescence properties of the three types of as-prepared YVO₄:Eu³⁺,Bi³⁺ phosphors were studied in detail. The average diameters for the phosphor particles are 2-4 μm for HT method, 0.1-0.4 μm for SG method, and 0.5 μm for core-shell structured SiO₂/YVO₄:Eu³⁺,Bi³⁺ particles, respectively. Photoluminescence spectra show that effective energy transfer takes place between Bi³⁺ and Eu³⁺ ions in each type of as-prepared YVO₄:Eu³⁺,Bi³⁺ phosphors. Introduction of Bi³⁺ into YVO₄:Eu³⁺ leads to the shift of excitation band to the long-wavelength region, thus the emission intensities of ⁵D₀-⁷F₂ electric dipole transition of Eu³⁺ at 615 nm upon 365 nm excitation increases sharply, which makes this phosphor a suitable red-emitting materials that can be pumped with near-UV light emitting diodes (LEDs).     

Temperature dependence of impurity quenched luminescence in Tm:LiLuF4

The study of the optical properties of a LiLuF₄ crystal doped with Tm³⁺ yielded the discovery of a strong temperature dependence of the Tm-Tm diffusion coefficient. Spectroscopic characteristics have been investigated as a function of the sample temperature, with particular regard to the luminescence decay following pulsed excitation. An appreciable excitation of the lifetime of the ³F₄ manifold is observed over the temperature range 8.9-298 K. The Judd-Ofelt calculations point out a radiative lifetime considerably longer than the experimental one. These facts suggest a theoretical interpretation based on the presence of impurities that quench the manifold and on a temperature-dependent energy migration between Tm³⁺ ions. A one-parameter best fit of the experimental measurements strongly confirms this hypothesis. Weak OH⁻ ion concentration is detected by means of IR and UV spectra, thus supporting the theoretical interpretation.     

Thermoluminescence studies of LiBa2B5O10:RE (RE=Dy, Tb and Tm)

LiBa₂B₅O₁₀:RE³⁺ (RE=Dy, Tb and Tm) was synthesized by the method of high-temperature solid-state reaction and the thermoluminescence (TL) properties of the samples under the irradiation of the γ-ray were studied. The result showed that Dy³⁺ ion was the most efficient activator. When the concentration of Dy³⁺ was 2 mol%, LiBa₂B₅O₁₀:Dy³⁺ exhibited a maximum TL output. The kinetic parameter of LiBa₂B₅O₁₀:0.02Dy was estimated by the peak shape method, for which the average activation energy was 0.757 eV and the frequency factor was 1.50×10⁷ s⁻¹. By the three-dimensional (3D) TL spectrum, the TL of the sample was contributed to the characteristic f-f transition of Dy³⁺. The dose-response of LiBa₂B₅O₁₀:0.02Dy to γ-ray was linear in the range from 1 to 1000 mGy. In addition, the decay of the TL intensity of LiBa₂B₅O₁₀:0.02Dy was also investigated.     

Comparative structural and photoluminescent study of Eu-doped La2O3 and La(OH)3 nanocrystalline powders

Eu³⁺-doped La₂O₃ nanocrystalline powder was prepared by polymer complex solution method and further used for preparation of Eu³⁺-doped La(OH)₃. Structural and optical characterization was carried out by powder X-ray diffraction and photoluminescent spectroscopy. XRD measurements confirmed the formation of hexagonal La₂O₃ and its recrystallization into La(OH)₃ in a humid atmosphere. Excitation spectra show redshift of host lattice and charge transfer emission bands in La(OH)₃ while bands that correspond to Eu³⁺f–f transitions are placed at same wavelengths in both samples. Photoluminescence spectra recorded over the temperature range from 10 K to 300 K show that intensities of emission lines in Eu³⁺-doped La₂O₃ do not depend on temperature as much as in La(OH)₃ sample. Observed dominant ⁵D₀→⁷F₂ and markedly visible ⁵D₀→⁷F₀ emissions in doped La₂O₃ indicate that Eu³⁺ ion is located in a structural site without an inversion center. On the other hand, in Eu³⁺-doped La(OH)₃⁵D₀→⁷F₀ transition is barely visible while ⁵D₀→⁷F₂ is not prominent, and with temperature drop three ⁵D₀→⁷F_J (J=1, 2, 4) transitions become almost of the same intensity. In both La₂O₃ and La(OH)₃ structures Eu³⁺ ion replaces La³⁺ in non-centrosymmetric C_3v and C_3h crystallographic sites, respectively, and difference in symmetry of the crystal field around europium ion is explained by comparing shape and volume of these sites. Decay times of the ⁵D₀- level recorded over the temperature range 10−300 K revealed that emission lifetime values in La₂O₃ (~0.7 ms) are almost two times higher than in La(OH)₃ (~0.4 ms), and unlike in La₂O₃, lifetime in La(OH)₃ is temperature dependent.     

Studies on the influence of lithium incorporation in the photoluminescence of Y2O3:Eu thin films

Nanostructured europium-doped yttrium oxide thin films with lithium as a co-dopant were prepared using pulsed laser ablation technique. X-ray diffraction studies of the films indicated amorphous nature of the as deposited films and a transformation to crystalline phase with increase of annealing temperature. In this transformation, lithium co-doped films showed early crystallization. Lithium substitution resulted not only in enhancement of photoluminescence at 612 nm, resulting from ⁵D₀-⁷F₂ transition within europium, but also found to reduce the required processing temperature for intense photoemission. The deviation observed in the value of lattice constant of films annealed at different temperatures is found to be sensitive to annealing temperature. In the light of this, the dependence of photoluminescence intensity on the magnitude of lattice imperfection is also discussed. The morphology and transmittance of the films are also found to be sensitive to annealing process and lithium doping.     

Optical gain due to the Eu transition in the alloy of Ca1-xEuxGa2S4

Room temperature photoluminescence quantum efficiency of the alloy of Ca_1−xEu_xGa₂S₄ was measured as a function of x, and was found to be nearly unity under excitation at peak wavelength of excitation spectrum (510 nm) in the x range of 0.01≤x≤0.2. At larger x values, it tends to decrease, but still as high as 30% for stoichiometric compound EuGa₂S₄. Taking these backgrounds into account, pump-probe experiments were done with Ca_1−xEu_xGa₂S₄ for searching optical gain at x=0.2. The optical gain of nearly 30 cm⁻¹ was confirmed to exist, though the pumping induced transient absorption which seems to limit the higher gain was found.     

New spectroscopic results of trivalent chromium in magnesium gallate

Cr³⁺ centers in MgGa₂O₄ powder samples are investigated by excitation and emission spectroscopic measurements at 4.2, 77 and 300 K. The ²E(²G)→⁴A₂ (⁴F) and ⁴T₂(⁴F)→⁴A₂(⁴F) electronic transitions are observed in the red and infrared regions and associated with chromium trivalent ions in octahedral sites. The results show that the material presents both high and intermediate crystal fields for these ions. The crystal-field parameter, Dq, and Racah parameters, B and C, are determined from the measurements.     

Comparison of different NaGdF4:Eu synthesis routes and their influence on its structural and luminescent properties

Eu³⁺:NaGdF₄ samples were obtained via co-precipitation in aqueous solution (CP), reversed micelle (RM) method, reaction between solid GdF₃ and NaF solution (SR) as well as a solid-state reaction at high temperatures (SS). The synthesised materials were characterised using X-ray powder diffractometry, TEM microscopy, infrared spectroscopy and TGA analysis. For discussion of optical properties excitation and emission spectra were recorded and emission decay times were measured. The CP and RM methods allow to obtain powders with crystallite size of ∼10 nm, which may be smoothly increased to about 1 μm during post-fabrication heat treatment. Differences in structural and especially in optical properties of phosphors prepared by different techniques are emphasised and applicability of wet-chemistry routes for synthesis of fluoride powders is argued.     

A simple photochemical method to synthesize Ga2O3-Dy-M thin films and their evaluation as optical materials (where M=Cr or Co)

We report the photochemical method to synthesize Ga₂O₃-Dy³⁺-Co³⁺ and Ga₂O₃-Dy³⁺-Cr³⁺ thin films. X-ray photoelectron spectroscopy, X-ray diffraction and photoluminescence were used to characterize the products. These analyses revealed that as-deposited and annealed films are amorphous. The optical characterization of the films showed that these are highly transparent in the visible spectrum but decrease significantly with doped and co-doped films. Under the excitation of UV light (254 nm) the doped films (Ga₂O₃-Dy³⁺) show the characteristic emissions of Dy³⁺ at 500, 575, 594, 605 and 652 nm corresponding to ⁴F_9/2→⁶H_J ( J=15/2, 13/2 and 11/2) transitions but the emissions decrease with the co-doped films (Ga₂O₃-Dy³⁺-M³⁺, where M=Cr or Co); a possible emission mechanism and energy transfer have been proposed.     

Absorption and emission of light in spark-processed silicon

Spark-processed Si (sp-Si) exhibits blue, green and red photoluminescence at around 385, 525 and 650 nm, depending on the wavelength of excitation. Its optical absorption spectrum reveals bands peaked approximately at 245, 277, 325 and 389 nm. The centers where absorption takes place were modeled as Si and silica clusters in an amorphous SiO_xN_y matrix using various embedding schemes. Geometry optimizations were applied prior to calculations of the absorption spectra of the clusters. The measured absorption spectrum of sp-Si and calculated absorption spectra were compared. Best agreement is achieved for Si particles embedded in amorphous SiO_xN_y matrix. The importance of the various embedding schemes is discussed and conclusions for the centers of emission are established.     

Combustion synthesis and photoluminescence of Eu, Dy-doped La2Zr2O7 nanocrystals

A facile and energy saving sol-gel combustion method has been used to prepare La₂Zr₂O₇ nanocrystallines. The pyrochlore La₂Zr₂O₇ nanocrystals have been obtained at a relatively low temperature with the grain size ranging from 45 to 70 nm. Eu³⁺ and Dy³⁺ have been introduced into the La₂Zr₂O₇ crystal structure, respectively, and the intense photoluminescence was observed. The relative intensity of electric dipole transition and magnetic dipole transition is considered for luminescence emission both of Eu³⁺ and Dy³⁺. The dependence of luminescence intensity on dopant concentration and the effect of Dy³⁺ co-doping on Eu³⁺ luminescence are also discussed.     

Compositional-dependent lead borate based glasses doped with Eu ions: Synthesis and spectroscopic properties

New multicomponent lead borate based glasses with various PbO/B₂O₃ weight ratio were prepared. The glass samples were analyzed in detail by using Raman and IR absorption spectroscopy. Optical properties of Eu³⁺ ions have been investigated in lead borate based systems, in which PbO/B₂O₃ weight ratios were changed from 1:2 to 8:1 in glass composition. The values of the phonon energy of the host and ⁵D₀ lifetime of Eu³⁺ decrease, whereas absorption and emission intensities, as well as bonding parameter increase with increasing PbO concentration. Additionally, spectral lines are shifted in direction to the lower frequency region. Non-monotonic dependence of the fluorescence intensity ratio R (⁵D₀-⁷F₂/⁵D₀-⁷F₁) upon PbO/B₂O₃ content has been observed in contrast to bonding parameter that is also non-linear but monotonic. Some structural and spectroscopic aspects for Eu-doped lead borate based glasses are presented.     

Effect of Ce co-doping on KY3F10:Pr crystals

A spectroscopic investigation on the effect of Ce³⁺ co-doping in fluoride KY₃F₁₀:Pr³⁺ crystals is presented. In particular spectroscopic measurements of three different samples of KY₃F₁₀ crystal doped with 0.3at% Pr³⁺ and co-doped with 0at%, 0.17at% and 0.3at% Ce³⁺ are discussed. Details on the growth of the crystals are also reported. Measurements were performed in the temperature range 10-300 K. Fluorescence and lifetime measurements have shown a cross relaxation between ³P₀-¹D₂ levels of Pr³⁺ and ²F_7/2-²F_5/2 of Ce³⁺. Data exhibit that this effect is strictly related to the Cerium concentration.     

Infrared luminescence from spark-processed silicon

The infrared (IR) photoluminescence (PL) emission of spark-processed silicon (sp-Si) was investigated. A broad and strong room temperature PL peak in the 945 nm (1.31 eV) spectral range was observed when sp-Si was excited with an argon laser. This peak is different from the PL commonly reported for anodically etched porous silicon and other silicon-based materials. The PL intensity increases substantially after annealing sp-Si between 350 and 500 °C in air after which it decreases again. The PL wavelength is observed to peak at 1010 nm by annealing sp-Si near 450 °C. It was further found that the most efficient PL occurs for a Si/O ratio of 0.3, for a small spark gap of about 1 mm, and for spark-processing times in the 15-60 min range.A model for the IR PL is proposed which mirrors that for visible PL. Specifically, it is proposed that the electrons which have been pumped by the laser from the ground state into a broad quasi-absorption band (or closely spaced absorption lines between 1.7 and 2.3 eV) revert back to lower IR levels at 1.31 eV by a non-radiative transition from where they revert radiatively to the ground state by emitting the observed 945 nm light.     

Influence of morphology on the emissive properties of dye-doped PVP nanofibers produced by electrospinning

Dye-doped polymer micro- and nanofibers with tailored light emission properties have great potential for applications in optical, optoelectronic, or photonic devices. In this study, these types of structures were obtained by electrospinning rhodamine 6 G-doped polyvinylpyrrolidone (PVP) using a polymer solution of 10% (mass) concentration in ethanol. Polymer nanofibers with different morphologies (smooth and beaded) and diameters of about 500 nm were obtained using different electrospinning conditions with the same solutions. Fluorescence optical microscopy observations showed that the dye was distributed uniformly in the doped PVP nanofibers. Different shifts were observed when we compared the wavelength of the dye emission band peak of the smooth nanofibers (566 nm) and the wavelength of the dye emission band peak of the beaded fibers (561.5 nm) produced by electrospinning in different conditions with the wavelength of the emission band peak for transparent thin films produced by spin coating (558 nm) using the same polymer solution. This demonstrates that it is possible to tune the optical properties of electrospun dye-doped polymer nanofibers simply by modifying the morphology of the material, i.e., the parameters of the electrospinning process.     

The photoluminescent properties of Eu in MgO-Ga2O3-SiO2 nanocrystalline glass-ceramic

The MgO-Ga₂O₃-SiO₂ glass-ceramic (GC) containing MgGa₂O₄ nanocrystals and glasses doped with Eu³⁺ ions were prepared by the sol-gel method. The down-conversion and up-conversion luminescence (UCL) properties were studied. The results indicated that the relative intensity of f-f transitions of Eu³⁺ decreased in contrast with that of charge transfer (CT) absorption with the increase in heating temperature. Using a Xe lamp and 800 nm femtosecond (fs) laser excitation, strong red luminescence of Eu³⁺ in MgO-Ga₂O₃-SiO₂ glasses and GC was observed.