Anisotropic nonlinear optical absorption of gold nanorods in a silica matrix

Nanocomposite films consisting of gold nanospheres or gold nanorods embedded in a silica matrix have been prepared using a hybrid deposition technique consisting of plasma-enhanced chemical vapor deposition of SiO₂ and co-sputtering of gold, followed by annealing at 900 °C. Subsequent irradiation with 30 MeV heavy ions (Cu⁵⁺) was used to form gold nanorods. Linear and nonlinear optical properties of this material are closely related with the surface plasmon resonance in the visible. The nonlinear absorption coefficient (α₂@532 nm) for the films containing gold nanospheres was measured by Z-scan and P-scan techniques, and it was found to be isotropic and equal to −4.8 × 10⁻² cm/W. On the contrary, gold nanorods films exhibited two distinct surface plasmon resonance absorption bands giving rise to a strong anisotropic behavior, namely a polarization-dependent linear absorption and saturable absorption. Z-scan and P-scan measurements using various light polarization directions yielded nonlinear absorption coefficient (α₂@532 nm) values varying from −0.9 × 10⁻² cm/W up to −3.0 × 10⁻² cm/W. Linearity of the P-scan method in the context of nanocomposite saturable absorption is also discussed.     

Photophysical and photoluminescence properties of co-activated ZnS:Cu,Mn phosphors

ZnS:Cu,Mn phosphors were prepared by conventional solid state reaction with the aid of NaCl-MgCl₂ flux at 900 °C. The samples were characterized by X-ray powder diffraction, UV-vis absorbance spectra and photoluminescence spectra. All samples possess cubic structure. Cu has a much stronger effect on the absorption property of ZnS than Mn. Incorporation of Mn into ZnS host only slightly enhances the light absorption, while addition of Cu remarkably increases the ability of absorption due to ground state Cu⁺ absorption. The emission spectra of the ZnS:Cu,Mn phosphors consist of three bands centered at about 452, 520 and 580 nm, respectively. Introduction of Mn significantly quenches the green luminescence of ZnS:Cu. The excitation energy absorbed by Cu is efficiently transferred to Mn activators non-radiatively and the Mn luminescence can be sensitized by Cu behaving as a sensitizer (energy donor).     

On the spectra luminescence properties of charoite silicate

Charoite is a hydrous alkali calcium silicate mineral [K₄NaCa₇Ba_0.75Mn_0.2Fe_0.05(Si₆O₁₅)₂(Si₂O₇)Si₄O₉(OH)·3(H₂O)] exhibiting an intense lilac colour related to Mn²⁺ and Fe³⁺ colour centres. These ions also contribute to a strong luminescence at ∼585 and 705 nm. This work studies the thermal dependence of these luminescent centres by (i) thermoluminescence (TL) of pre-heated and pre-irradiated charoite aliquots, (ii) by time-resolved cathodoluminescence (TRS-CL) at room and cryogenic temperatures (RT and CT), (iii) by spatially resolved spectra CL under scanning electron microscopy (SRS-CL-SEM) and (iv) by ion beam spectra luminescence (IBL) with H⁺, H₂⁺ and ⁴He⁺ ions at RT and LT. The main peak, ∼585 nm, is linked to a transition ⁴T_1,2 (G)→⁶A₇(S) in Mn²⁺ ions in distorted six-fold coordination and the emission at ∼705 nm with Fe²⁺→Fe³⁺ oxidation in Si⁴⁺ lattice sites. Less intense UV-blue emissions at 340 and 390 nm show multi-order kinetic TL glow curves involving continuous processes of electron trapping and de-trapping along with an irreversible phase transition of charoite by de-hydroxylation and lattice shortening of Δa=0.219 Å, Δb=0.182 Å; Δc=0.739 Å. The Si-O stressed lattice of charoite has non-bridging oxygen or silicon vacancy-hole centres, and Si-O bonding defects which seem to be responsible for the 340 nm emission. Extrinsic defects such as the alkali (or hydrogen)—compensated [AlO₄/M⁺] centres could be linked with the 390 nm emission. Large variations in 585 and 705 nm intensities are strongly temperature dependent, modifying local Fe-O and Mn-O bond distances, short-range-order luminescence centres being very resistant under the action of the heavy ion beam of ⁴He⁺. The SRS-CL demonstrates strong spatial heterogeneity in the luminescence of the charoite.     

First-principles study on electronic structures of BaWO4 crystals containing F-type color centers

The electronic structures of BaWO₄ crystals containing F-type color centers are studied within the framework of the fully relativistic self-consistent Dirac-Slater theory, using a numerically discrete variational (DV-Xα) method. It is concluded that F and F⁺ color centers have donor energy level in the forbidden band. The optical transition energies are 2.449 and 3.101 eV, which correspond to the 507 and 400 nm absorption bands, respectively. It is predicted that 400-550 nm absorption bands originate from the F and F⁺ color centers in BaWO₄ crystals.     

Enhanced photo-response of thin-film structures with nanocrystals

Thin-film multilayers with dielectric and semiconductor nanolayers of 200-10 nm thicknesses have been deposited by thermal evaporation onto irradiation-resistive substrates using pure crystals as evaporated targets. Some multilayers were γ-irradiated in air at room temperature with dose of 83 kGy. X-ray diffraction and microscopy studies reveal that the multilayers consist of nanometer-sized crystals with cubic structure and defined size. Film structures were oriented along the (1 1 1) plane. Absorption spectra of non-irradiated LiF nanocrystals of 100 nm size and those of initial crystals give evidence of metal colloids presence. Photoluminescence spectra of γ-irradiated nanostructures with various LiF content show the enhancement of F₃⁺-colour centres excitation in the region of metal colloids absorption and the increase is observed between emission intensities of F₃⁺ and F₂ centers with respect to initial crystals γ-coloured in identical conditions. Emission intensities of both centers under excitation in the M band correlate with LiF content. These effects, which are related to high-quality nanocrystals, but at the same time depend strongly on the defect content, especially as far as their 1-2 ps nonlinearities are concerned, could depend on nanocrystal purity and metal excess collection in their boundaries regions.     

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.     

Preparation, characterization and study of optical properties of ZnS nanophosphor

In this work the preparation, characterization and photoluminescence studies of pure and copper-doped ZnS nanophosphors are reported, which are prepared by using solid-state reaction technique at a temperature of 100 °C. The as-obtained samples were characterized by X-ray diffraction (XRD) and UV-VIS Reflectance spectroscopy. The XRD analysis confirms the formation of cubic phase of undoped as well as Cu²⁺-doped ZnS nanoparticles. Furthermore it shows that the average size of pure as well as copper-doped samples ranges from 15 to 50 nm. The room-temperature PL spectra of the undoped ZnS sample showed two main peaks centered at around 421 and 450 nm, which are the characteristic emissions of interstitial zinc and sulfur vacancies, respectively. The PL of the doped sample showed a broad-band emission spectrum centered at 465 nm accompanied with shoulders at around 425, 450 and 510 nm, which are the characteristic emission peaks of interstitial zinc, sulfur vacancies and Cu²⁺ ions, respectively. Our experimental results indicate that the PL spectrum confirms the presence of Cu²⁺ ions in the ZnS nanoparticles as expected.     

Luminescence and defects creation under photoexcitation of CsI : Tl crystals in Tl-related absorption bands

Characteristics of the defects created at 4.2 K by the UV-irradiation of CsI : Tl crystals in the Tl⁺-related absorption bands (by photons of 5.8-4.8 eV energy) have been studied. The dependences of the intensities of the thermally stimulated luminescence peaks appearing near 60, 90 and 125 K and of the recombination luminescence photostimulation bands peaking at 2.35, 1.92, 1.33 and 0.89 eV on the irradiation energy and duration, uniaxial stress and thallium concentration have been examined. The mechanisms of the processes, responsible for the appearance of the intense visible (2.55 and 2.25 eV) luminescence of excitons localized near Tl⁺ ions and creation of defects pairs of the type of Tl⁰-V_K and Tl⁺-V_K with various distances between the components, have been discussed.     

Emission color variation of M2SiO4:Eu (M=Ba, Sr, Ca) phosphors for light-emitting diode

The luminescent properties of alkaline earth orthosilicates M₂SiO₄ (M=Ba, Sr, Ca) doped with Eu²⁺ ions are investigated. Two emission bands are assigned to the f-d transitions of Eu²⁺ ions doped into two different cation sites in host lattices confirmed by electron paramagnetic resonance signal. Two emission bands show the different emission color variation with substituting M²⁺ cations with smaller cations. This behavior is discussed in terms of two competing factors of the crystal field strength and covalence. Also the decay times are in order of 600-1000 ns. These phosphors with maximum excitation of around 370 nm can be applied as a color-tunable phosphor for light-emitting diode based on ultraviolet chip/phosphor technology.     

Growth and spectral properties of Nd:GdVO4 laser crystal

In this paper, the Czochralski growth, absorption spectra, and photoluminescence spectra of Nd:GdVO₄ crystals are studied. From its absorption spectra, Nd:GdVO₄ is found to exhibit an anisotropic optical absorption effect, and its effective Judd-Ofelt parameters are calculated: Ω₂=10.281×10⁻²⁰ cm², Ω₄=5.426×10⁻²⁰ cm² and Ω₆=9.943×10⁻²⁰ cm². By these parameters, the absorption oscillator strengths, emission oscillator strengths, transition probabilities, fluorescence branch ratios, energy lifetimes, and integrated emission cross-sections are also derived. The photoluminescence spectra of Nd:GdVO₄ crystal consist of a wide emission band of host and the characteristic emission bands of Nd³⁺. Based on the excitation spectrum, both the two evident peaks locating at 345 and 371 nm are ascribed to the characteristic excitation of Nd³⁺, and an energy transfer from the host to its doping Nd³⁺ ions is indicated.     

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.     

Preparation and optical properties of Cu2O hollow microsphere film and hollow nanosphere powder via a simple liquid reduction approach

In this work, we report a simple liquid reduction approach to prepare Cu₂O hollow microsphere film and hollow nanosphere powder with Cu(OH)₂ nanorods as precursor and ascorbic acid as the reductant at 60 °C. When Cu(OH)₂ nanorod array film grown on a copper foil is used as the precursor, Cu₂O thin film made up of hollow microspheres with average diameter of 1.2 μm is successfully prepared. When the Cu(OH)₂ nanorods are scraped from the copper foil and then used as the precursor, Cu₂O hollow nanosphere powder with the average diameter of 270 nm is obtained. The samples are characterized by X-ray powder diffraction (XRD), field-emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM) and ultraviolet-vis light (UV-vis) absorption spectra. A possible formation mechanism of Cu₂O hollow spheres is discussed.     

Analysis of the effect of annealing on the photoluminescence spectra of Cu ion implanted ZnS nanoparticles

In the present study, we report the photoluminescence (PL) study of nanoparticles of ZnS implanted with Cu⁺ ions at the doses of 5×10¹⁴, 1×10¹⁵ and 5×10¹⁵ ions/cm² and annealed at 200 and 300 °C. The photoluminescence spectra of the samples implanted at lower doses of 5×10¹⁴ and 1×10¹⁵ ions/cm² and annealed at 200 and 300 °C showed peaks at around 406, 418 and 485 nm. The PL emission peak at 485 nm was attributed to the transition of electrons from conduction band of ZnS to the impurity level formed by the implanted Cu⁺ ions. In the PL spectrum of the sample implanted at the highest dose of 5×10¹⁵ ions/cm², in addition to the emission peaks observed in the PL spectra of the samples implanted at lower doses, a peak at around 525 nm, the intensity of which decreased with increase in the annealing temperature, was observed. The emission peak at 525 nm was attributed to the transitions between sulfur and zinc vacancy levels. The full width at half maximum (FWHM) of the emission peak at 406 nm was observed to decrease with increase in annealing temperature, indicating lattice reconstruction. The observation of copper ion impurity related peak at 485 nm in the PL spectra of samples of the present study indicated that the doping of copper ions into the ZnS lattice is achievable by implanting Cu⁺ ions followed by annealing.     

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.     

Nonlinear optical properties of Cu nanoclusters by ion implantation in silicate glass

Metal nanocluster composite glass prepared by 180 keV Cu ions into silica with dose of 1 × 10¹⁷ ions/cm² has been studied. The microstructural properties of the nanoclusters were analysed by optical absorption spectra and transmission electron microscopy (TEM). Third-order nonlinear optical properties of the nanoclusters were measured at 1064 nm and 532 nm excitations using Z-scan technique. The nonlinear refraction index, nonlinear absorption coefficient, and the real and imaginary parts of the third-order nonlinear susceptibility were deduced. The mechanisms responsible for the nonlinear response were discussed. Absolute third-order nonlinear susceptibility χ⁽³⁾ of this kind of sample was determined to be 2.1 × 10⁻⁷ esu at 532 nm and 1.2 × 10⁻⁷ esu at 1064 nm, respectively.     

Energy transfer in LaMgB5O10:Pr,Mn under VUV excitation

Luminescent properties of Pr³⁺ or Mn²⁺ singly doped and Pr³⁺, Mn²⁺ co-doped LaMgB₅O₁₀ are investigated by synchrotron radiation VUV light. When LaMgB₅O₁₀:Pr³⁺ is excited at185 nm, the photon cascade emission between 4f levels of Pr³⁺ is observed. In the excitation spectra of LaMgB₅O₁₀:Mn²⁺ monitoring the 615 nm emission of Mn²⁺, several excitation bands in a spectral range from 330 to 580 nm are recorded, among which the most intense band is centered at 412 nm (⁶A_1g→⁴E_g-⁴A_1g). This band has considerable spectra overlap with the 410 nm emission (¹S₀→¹I₆) of Pr³⁺, which is favorable for energy transfer from Pr³⁺ to Mn²⁺. Such energy transfer is observed in the co-doped sample, converting the violet emission (410 nm) of Pr³⁺ into the red emission (615 nm) of Mn²⁺. The concentration dependence of transfer efficiency is also investigated.     

Thermal stability and spectroscopic properties of Er-doped lead fluorogermanate glasses

The thermal characterization and spectroscopic properties of Er³⁺-doped 0.6GeO₂-(0.4-x)PbO-xPbF₂ glasses were investigated experimentally. With the replacement of PbO by PbF₂ the thermal stability of glasses is improved and the infrared fluorescence intensity at 1530 nm is increased. The Judd-Ofelt intensity parameters, radiative transition rates, and fluorescence lifetimes of the excited ⁴I_13/2 level of Er³⁺ ions were calculated from Judd-Ofelt theory. The asymmetric ligand field around Er³⁺ ions resulted from the incorporation of PbF₂ into germanate glasses, broadens the infrared emission spectra at 1530 nm. Upconversion luminescence in the investigated glasses was observed at room temperature under the excitation of 976 nm laser diode. The glass 0.6GeO₂-0.3PbO-0.1PbF₂ exhibits the maximum upconversion emission intensity, while no frequency upconversion luminescence was observed in the 0.6GeO₂-0.4PbO glass. The quadratic dependence of the green and red emissions on excitation power indicates that two-photon absorption contributes to the visible emission under the 976-nm excitation.     

Optical absorption and emission properties of Gd in silica host

We present a study of the optical properties of Gd-doped sol-gel silica glasses densified at different temperatures (from 450 up to 1050 °C) by means of optical absorption (OA) and radio luminescence (RL). The effect of a post-densification rapid thermal treatment (RTT) at approximately 1800 °C is also considered. Room temperature OA and RL measurements have revealed a slight low-energy shift of Gd³⁺ absorption/emission lines by densification temperature increasing accompanied by a parallel increase of Gd³⁺ RL intensities, especially strong after RTT. These effects are interpreted on the basis of structural modifications of the silica matrix and of the removal of non-radiative channels competing with Gd³⁺ emission. Moreover, RL spectra of fully densified samples display high-energy shoulders on the ⁶P_7/2-⁸S Gd³⁺ emission possibly related to crystal field splitting of the ⁶P_7/2 state. This interpretation is supported by the temperature dependence of RL spectra, investigated in the 10-320 K temperature interval: an increase of the intensity of high-energy components vs. temperature has been observed, which can be interpreted as due to thermally assisted excitation of electrons belonging to the lower ⁶P_7/2 state to higher crystal field states and their subsequent radiative recombination.     

Ion irradiation induced Al-Ti interaction in nano-scaled Al/Ti multilayers

Interactions induced in Al/Ti multilayers by implantation of Ar ions at room temperature were investgated. Initial structures consisted of (Al/Ti) × 5 multilayers deposited by d.c. ion sputtering on Si(1 0 0) wafers, to a total thickness of ∼250 nm. They were irradiated with 200 keV Ar⁺ ions, to the fluences from 5 × 10¹⁵ to 4 × 10¹⁶ ions/cm². It was found that ion irradiation induced a progressed intermixing of the multilayer constituents and Al-Ti nanoalloying for the highest applied fluence. The resulting nanocrystalline structure had a graded composition with non-reacted or interdiffused Al and Ti, and γ-AlTi and AlTi₃ intermetallic phases. Most intense reactivity was observed around mid depth of the multilayers, where most energy was deposited by the impact ions. It is presumed that Al-Ti chemical reaction is triggered by thermal spikes and further enhanced by chemical driving forces. The applied processing can be interesting for fabrication of tightly bond multilayered structures with gradual changes of their composition and properties.     

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.