Characterization of Standard Reference Material 2940, Mn-ion-doped glass, spectral correction standard for fluorescence

Standard Reference Material (SRM) 2940 is a cuvette-shaped, Mn-ion-doped glass, recommended for use for relative spectral correction of emission and day-to-day performance validation of steady-state fluorescence spectrometers. Properties of this standard that influence its effective use or contribute to the uncertainty in its certified emission spectrum were explored here. These properties include its photostability, absorbance, dissolution rate in water, anisotropy, temperature coefficient of fluorescence intensity, and fluorescence lifetimes. Long and short lifetime components of the fluorescence displayed different emission spectra, making the certified spectrum useful with fluorescence instruments employing continuous excitation only. The expanded uncertainties in the certified spectrum are about 5% around the peak maximum at 620 nm, using an excitation wavelength of 412 nm. The SRM also exhibits a strong resistance to photodegradation, with no measurable decrease in fluorescence intensity even after 17 h of irradiation with the visible light from a Xe lamp.     

Characterization of Standard Reference Material 2941, uranyl-ion-doped glass, spectral correction standard for fluorescence

Standard Reference Material^® (SRM^®) 2941 is a cuvette-shaped, uranyl-ion-doped glass, recommended for use for relative spectral correction of emission and day-to-day performance validation of fluorescence spectrometers. Properties of this standard that influence its effective use or contribute to the uncertainty in its certified emission spectrum have been explored here. These properties include its photostability, absorbance, dissolution rate in water, anisotropy, temperature coefficient of fluorescence intensity, and fluorescence lifetimes. The expanded uncertainties in the certified spectrum are about 4% around the peak maximum at 526 nm, using an excitation wavelength of 427 nm. The SRM also exhibits a strong resistance to photodegradation, with no measurable decrease in fluorescence intensity even after 8 h of laser irradiation.     

Characterization of Standard Reference Material 2943, Cu-ion-doped glass, spectral correction standard for blue fluorescence

Standard Reference Material (SRM) 2943 is a cuvette-shaped, Cu-ion-doped glass, recommended for use for relative spectral correction of emission and day-to-day performance verification of steady-state fluorescence spectrometers. Properties of this standard that influence its effective use or contribute to the uncertainty in its certified emission spectrum were explored here. These properties include its photostability, absorbance, dissolution rate in water, anisotropy and temperature coefficient of fluorescence intensity. The expanded uncertainties in the certified spectrum are about 5% around the peak maximum at 446 nm, using an excitation wavelength of 330 nm. SRM 2943 can replace SRM 936a quinine sulfate dihydrate, which is no longer sold by NIST, for many applications, as it covers the same spectral range. SRM 2943 is significantly more photostable than organic dyes, but unlike the other fluorescent glass SRMs in this series, it does photodegrade gradually under lamp-based excitation.     

Intramolecular energy and charge transfer in 5-(9-anthryl)-3-(4-nitrophenyl)-1-phenyl-2-pyrazoline

The absorption and photoluminescence of the newly synthesized 5-(9-anthryl)-3-(4-nitrophenyl)-1-phenyl-2-pyrazoline (AN PP) were investigated. The absorption is the absorption of anthryl moiety at about 325-400 nm, superimposed on the broader absorption of 3-(4-nitrophenyl)-1-phenyl-2-pyrazoline moiety peaked at 420 nm. On excitation at 420 nm, the fluorescence spectrum has only one emission band from the pyrazoline moiety. This emission band exhibits a larger red shift with an increase in the polarity of solvents. But on excitation at 365 nm, the fluorescence spectrum has two emission bands coming from the anthryl and pyrazoline moieties, respectively. The intensity ratio of the two bands is different in solvents of different polarity. It is concluded that photo-induced intramolecular energy transfer from the anthryl to pyrazoline moiety exists simultaneously with the charge transfer from N (1) to C (3) in the pyrazoline moiety in the excited state and both compete with each other.     

Optical and photophysical investigation of Meso, Proto and Hematoporphyrin(IX)dimethylester doped hybrid borate glasses

Hybrid borate glasses containing different concentrations (0.5-2.0 mg in 12 g of boric acid) of Mesoporphyrin(IX)dimethylester, Protoporphyrin(IX)dimethylester and Hematoporphyrin(IX)dimethylester were prepared by rapid melt quench technique at 230 °C. The hybrid glass samples were characterized by X-ray diffraction, optical absorption, steady state and time-resolved fluorescence emission. The optical absorption spectrum shows red-shift in Soret band along with change in Q-band pattern. The intensity of Q-band was found to increase with increase in the concentration of porphyrin in the glass. Steady state emission spectrum shows strong S₂→S₀ emission in the range 462-495 nm and blue shift in S₁→S₀ emission. Time-resolved fluorescence emission and fluorescence excitation spectra showed that different structures of porphyrins were exist in the glass samples. The variation in the spectral behaviour in the glass was correlated with those in solution medium and possible structures of porphyrin in borate glass were explored.     

Electronic absorption and emission spectra of Alq3 in solution with special attention to a delayed fluorescence

Tris(8-quinolinolato)aluminum(III) (Alq₃) shows electronic absorption bands at 378, 360 (in a 1:1 mixed solvent of methanol and ethanol (ME) at 77 K), 334, 316, 300, 263, 255.8, and 233 nm in ethanol at room temperature. According to the polarized fluorescence excitation spectrum together with MO calculations, for instance, the 360 nm band is assigned to an LL CT transition (an intramolecular charge transfer transition between two ligands), and the 378 nm band to an LM/ML CT one (an intramolecular charge transfer transition between ligand and metal). Alq₃ shows a broad fluorescence band peaking at around 478 nm in the ME matrix at 77 K. The emission spectrum measured with a phosphoroscope has two emission bands at 567 and 478 nm. The 567 nm band accompanies vibronic bands at 578 and 605 nm, being safely assigned to a phosphorescence of Alq₃. The lifetimes of the 478 and 567 nm bands are both 5.4 ms. The lifetime of the 478 nm band together with the band position and its band shape indicate that this band can be assigned to a delayed fluorescence.     

Two-color two-photon excitation of indole using a femtosecond laser regenerative amplifier

The fluorescence emission from indole resulting from two-color two-photon (2C2P) excitation with 400 and 800 nm wavelengths is observed, using the second harmonic and fundamental wavelength of a 800 nm 40 fs pulsed Ti:Sapphire femtosecond (fs) regenerative amplifier operating at a repetition rate of 1 kHz. By delaying one fs laser pulse relative to the other, the cross correlation of fluorescence is observed, which indicates the generation of 2C2P fluorescence signal in the experiment. The strongest 2C2P fluorescence emission characterized by the peak of cross correlation curve suggests optimal temporal overlap of the two fs laser pulses. The 2C2P fluorescence signal is linearly dependent on the total excitation intensity. The fluorescence signals with 400 nm and 800 nm irradiation alone are also demonstrated and discussed in this paper.     

Laser-induced fluorescence decays of polyethylene films

The fluorescence lifetime of photo-oxidative emission at 360 nm becomes shorter when stabilizer is added to polyethylene film. A broad emission band at 450 nm is attributed to the emission from a charge transfer complex. The preliminary results show that the quenching of photo-oxidative emission and the fluorescence intensity decay can be used to evaluate the extent of photo-stability of polyethylene films.     

White-light emission derived from yttrium tungstate-chloride xerogel without activator ions

White xerogel powder of yttrium tungstate-chloride was synthesized, and its photoluminescence properties were investigated. Under the excitation of 254 nm, the xerogel phosphor exhibits emission ranging from 300 to 650 nm. This luminescent spectrum is identified as two emission bands of 300-400 and 400-650 nm due to different emission mechanism. While the emission band of 300-400 nm is ascribed to the charge transfer (CT) from O to metal W, the emission of 400-650 nm is attributed to electron-hole (e⁻-h⁺) carrier emission related to oxygen vacancies. By calcining the sample in reducing atmosphere, the number of oxygen vacancies acting as luminescence centers is increased. As a result, the emission intensity of 400-650 nm is significantly enhanced. Based on electron paramagnetic resonance and spectral analysis, the mechanism of peroxy-radical hole traps (PRHT) is proposed for the luminescence of 400-650 nm.     

Control of emission peaks of X-ray phosphor using dye-silica nanoparticles

Simple method yielding new emission peaks to the X-ray phosphor and its mechanism were investigated using concentrated-dye-molecule-doped silica nanoparticles (dye-silica nanoparticles) and X-ray phosphors. The dye-silica nanoparticles were coated on the sheet of the X-ray phosphor using 20 wt% polyvinyl alcohol solution. The fluorescence of the dye-silica nanoparticle coated onto X-ray phosphor was successfully observed by X-ray irradiation. The fluorescent cascade from the X-ray-irradiated phosphor could be used in the excitation of the dye-silica nanoparticles by coating on the calcium tungstate (X-ray phosphor). The observed new fluorescence was based on the extent of the overlapping of wavelengths between the emission of the X-ray phosphor and the excitation of the dye-silica nanoparticles. The fluorescent peak of the calcium tungstate as the X-ray phosphor shifted from 434 to 425 nm. The dye-silica particle-calcium tungstate hybrid material showed new emission peaks from 543 to 601 nm due to the addition of fluorescein, rhodamine red-X, or cy5. The new emission peaks changed by the content of dye and the size of the silica nanoparticles. The fluorescence intensity ratio of the new fluorescence peaks at 543 nm against that of the X-ray phosphor depended on the fluorescent cascade from the X-ray-irradiated X-ray phosphor. It can closely match the overall emission of the phosphorous intensity screens to the sensitivity of the film allowing lower dose X-rays to obtain the same image clarity.     

Synthesis and fluorescence properties of pure and metal-doped spherical ZnS particles from EDTA-metal complexes

Monodispersed spherical ZnS particles as well as doped with Cu, Mn ions were synthesized from metal-chelate solutions of ethylenediamine tetraacetate (EDTA) and thioacetamide (TAA). The characterizations of the ZnS-based particles were investigated via TEM, SEM, XRD, TG/DTA and PL measurements. The sphere size was controlled from 50 nm to 1 μm by adjusting the nucleation temperatures and molar ratio of Zn-EDTA to TAA. The emission intensity continuously increased with the increase of the particle size. When the ZnS microspheres were annealed at 550-800 °C, there were two specific emission bands with the centers at 454 nm and 510 nm, which were associated with the trapped luminescence arising from the surface states and the stoichiometric vacancies, respectively. When Cu²⁺ was introduced into ZnS microspheres, the dominant emission was red-shifted from 454 to 508 nm, fluorescence intensity also sharply increased. However, for the Mn²⁺-doped ZnS, the emission intensity was significantly enhanced without the shift of emission site.     

Fluorescence properties of Ag nanoparticles in water, methanol and hexane

Ag nanoparticles, synthesized employing the electro-exploding wire technique, are reported. Absorption in the UV-visible region by these particles is characterized by the features reported in the literature, namely, a possible plasmon peak at ∼404 nm. For Ag nanoparticles dispersed in water, photo-excitation in the ranges 210-235 and 255-280 nm produces similar fluorescence emission at ∼300 nm, whose corresponding resonant absorption takes place at 215 and 270 nm in the excitation spectra. Further, we study the effect of the surrounding medium (solvent effect) on fluorescence from these nanoparticles by comparing fluorescence emission in methanol and hexane for photo-excitation in the same range. Compared to water, fluorescence emission in methanol is observed red-shifted at ∼310 nm, which further red-shifts to ∼325 nm in hexane. The corresponding resonant absorptions in methanol are at 225 and 275 nm. Consequence of this red-shift in a less polar solvent is discussed.     

Reversible UV degradation of PMMA plastic optical fibers

Laser-induced fluorescence, Raman and absorption spectroscopy are used to investigate reversible degradation of transmission in PMMA optical fibers. When exposed to 254 nm UV light, optical transmission of PMMA plastic optical fiber in 400-800 nm range shows a significant increase in attenuation for shorter wavelengths. Over a period of 10 days following UV exposure, the transmittance of the plastic fiber recovers to a significant fraction of its pre-exposure value. UV-exposed fiber exhibits strong laser-induced fluorescence with 488 nm argon-ion laser. This fluorescence spans a spectral region between 450 nm and 750 nm with a peak around 580 nm. The fluorescence intensity decreases over several days following UV exposure. Likewise, Raman is also used to investigate degradation process. Freshly UV-exposed fiber shows total absence of Raman spectrum of PMMA. Following UV exposure, recovery of Raman signal over several days is correlated to the recovery of fiber transmittance as well as the decay of laser-induced fluorescence. A widely believed plausible explanation for UV-induced increase of attenuation involves formation of different macro radicals which recombine progressively after UV is stopped. Laser-induced fluorescence over several days is reported here providing direct evidence for molecular-level deterioration and recovery of PMMA.     

Localized surface plasmon resonance enhanced blue light-emission of polyfluorene copolymer

Polyfluorene-based blue light-emitting devices suffer from the shortcomings of low stability, drastic loss of quantum yield and poor color purity. To find out the solution, we use silver nanoparticles for enhancement of photoluminescence of polyfluorene copolymer (PCFOz) through localized surface plasmon resonance (LSPR) coupling effect. The photoluminescence from PCFOz can be concentrated down to nanoscale, realizing a high spatial selectivity of the fluorescence enhancement process. PL emission of conjugated polymer is blueshifted about 8 nm from the peak emission of 433 nm for the neat PCFOz film to around 425 nm for the Ag/PCFOz composite film. The full width at half maximum of PCFOz is reduced from 88 to 60 nm. Absorbance spectra and time resolved photoluminescence measurements further demonstrate that both absorption intensity and recombination rate of PCFOz increase due to strong LSPR-excitons coupling. Optical properties of such plasmon-enhanced organic light emitters were also studied by temperature-dependent PL spectroscopy from 10 to 200 K. In comparison with bare PCFOz, the LSPR induced emission enhancement ratio significantly increases with increasing temperature. These results are believed to be important for the development of highly efficient blue organic light-emitting devices based on all-solution processing.     

Optical characterization of ZnO nanoparticles capped with various surfactants

The presence of surfactants (Hexamine, tetraethylammonium bromide (TEAB), cetyltrimethylammonium bromide (CTAB), tetraoctylammonium bromide (TOAB) and PVP) on the surface of zinc oxide (ZnO) nanoparticles resulted variation in their optical properties. The optical properties of each surfactant-capped zinc oxide nanoparticles were investigated using UV-visible absorption and fluorescence techniques. The particle size of these nanoparticles were calculated from their absorption edge, and found to be in the quantum confinement range. The absorption spectra and fluorescent emission spectra showed a significant blue shift compared to that of the bulk zinc oxide. Large reduction in the intensity of visible emission of zinc oxide/surfactant was observed and these emissions were vanished more quickly, with the decrease in excitation energy, for the smaller nanoparticles. Out of the four surfactants (other than PVP), CTAB-capped zinc oxide has smallest particle size of 2.4 nm, as calculated from the absorption spectrum. Thus the presence of surfactant on the surface of zinc oxide plays a significant role in reducing defect emissions. Furthermore, ZnO/PVP nanoparticles showed no separate UV emission peak; however, the excitonic UV emission and the visible emission at 420 nm overlap to form a single broad band around 420 nm.     

Surfactant assisted surface studies of zinc sulfide nanoparticles

We report a simple soft chemical method for the synthesis of ZnS nanoparticles using varying concentration of cationic surfactant CTAB and examine its surface properties. Powder X-ray diffraction, UV-vis spectroscopy, photoluminescence spectroscopy, selective area electron diffraction, and transmission electron microscopy are used to characterize the as prepared ZnS nanoparticles. XRD and TEM measurements show the size of polydispersed ZnS nanoparticles is in the range of 2-5 nm with cubic phase structure. The photoluminescence spectrum of ZnS nanoparticles exhibits four fluorescence emission peaks centered at 387 nm, 412 nm, 489 nm and 528 nm showing the application potential for the optical devices. In Raman spectra of ZnS nanoparticles, the modes around 320, 615 and 700 cm⁻¹ are observed.     

Photophysical parameters and fluorescence quenching of 7-diethylaminocoumarin (DEAC) laser dye

The optical properties including electronic absorption spectrum, emission spectrum, fluorescence quantum yield, and dipole moment of electronic transition of 7-diethylaminocoumarin (DEAC) laser dye have been measured in different solvents. Both electronic absorption and fluorescence spectra are red shifted as the polarity of the medium increases, indicating that the dipole moment of molecule increases on excitation. The fluorescence quantum yield of DEAC decreases as the polarity of solvent increases, a result of the role of solvent polarity in stabilization of the twisting of the intramolecular charge transfer (TICT) in excited state, which is a non-emissive state, as well as hydrogen bonding with the hetero-atom of dye. The emission spectrum of DEAC has also been measured in cationic (CTAC) and anionic (SDS) micelles, the intensity increases as the concentration of surfactant increases, and an abrupt change in emission intensity is observed at critical micelle concentration (CMC) of surfactant. 2×10⁻³ mol dm⁻³ of DEAC gives laser emission in the blue region on pumping with nitrogen laser (λ_ex=337.1 nm). The laser parameters such as tuning range, gain coefficient (α), emission cross section (σ_e), and half-life energy have been calculated in different solvents, namely acetone, dioxane , ethanol, and dimethyforamide (DMF). The photoreactivity of DEAC has been studied in CCl₄ at a wavelength of 366 nm. The values of photochemical yield (?_c) and rate constant (k) are determined. The interaction of organic acceptors such as picric acid (PA), tetracyanoethylene (TCNE), and 7,7,8,8-tetracynoquinonedimethane (TCNQ) with DEAC is also studied using fluorescence measurements in acetonitrile (CH₃CN); from fluorescence quenching study we assume the possible electron transfer from excited donor DEAC to organic acceptor forming non-emissive exciplex.     

Strong violet luminescence from ZnO nanocrystals grown by the low-temperature chemical solution deposition

The luminescence properties of zinc oxide (ZnO) nanocrystals grown from solution are reported. The ZnO nanocrystals were characterized by scanning electron microscopy, X-ray diffraction, cathodo- and photoluminescence (PL) spectroscopy. The ZnO nanocrystals have the same regular cone form with the average sizes of 100-500 nm. Apart from the near-band-edge emission around 381 nm and a weak yellow-orange band around 560-580 nm at 300 K, the PL spectra of the as-prepared ZnO nanocrystals under high-power laser excitation also showed a strong defect-induced violet emission peak in the range of 400 nm. The violet band intensity exhibits superlinear excitation power dependence while the UV emission intensity is saturated at high excitation laser power. With temperature raising the violet peak redshifts and its intensity increases displaying unconventional negative thermal quenching behavior, whereas intensity of the UV and yellow-orange bands decreases. The origin of the observed emission bands is discussed.     

Sensitive determination of enoxacin by its enhancement effect on the fluorescence of terbium(III)-sodium dodecylbenzene sulfonate and its luminescence mechanism

The fluorescence system of enoxacin-Tb³⁺-sodium dodecylbenzene sulfonate (SDBS) was investigated in this paper. The experiments indicated that the fluorescence intensity of Tb³⁺-SDBS was greatly enhanced by enoxacin. Accordingly, a sensitive fluorimetric method for determining enoxacin was established. The fluorescence intensity was measured by a 1-cm quartz cell with an excitation wavelength of 290 nm and an emission wavelength of 545 nm. The enhanced fluorescence intensity of the system (ΔF) showed a good linear relationship with the concentration of enoxacin in the range of 5.0×10⁻⁹ to 2.0×10⁻⁶ mol L⁻¹, its correlation coefficient was 0.9992 and the detection limit (S/N=3) was 2.8×10⁻⁹ mol L⁻¹. The presented method was used to determine enoxacin in real pharmaceutical samples. The luminescence mechanism was also discussed in detail. In the fluorescence system of enoxacin-Tb³⁺-SDBS, SDBS not only acted as the surfactant but also acted as the energy donor.     

Photoluminescence studies of Si/SiO2 nanoparticles synthesized with different laser irradiation wavelengths of nanosecond pulse duration

Photoluminescence (PL) properties of Si nanoparticles (Si-np) produced by irradiating the Si wafer with nanosecond laser pulses at 532, 683 and 1064 nm are studied. Si-np are found to be deposited in a doughnut shape around the irradiated spot. The irradiation wavelength is found to be the main cause for the particle size variation. Exposure of the freshly prepared Si-np to air for different periods of time leads to increased PL intensity reaching saturation after few days. The PL spectrum shows two well resolved peaks around 435 nm (2.85 eV) and 441 nm (2.81 eV) within an hour of exposure of the freshly prepared samples to air with broadening of the emission spectrum on further exposure to air. Possible mechanism of particle size variation and PL emission are discussed.