Role of various LB parameters on the optical characteristics of mixed Langmuir-Blodgett films

This communication reports the spectroscopic characterizations of mixed Langmuir-Blodgett (LB) films of non-amphiphilic N,N-bis (2,5-di-tert-butylphenyl)- 3,4,9-perylenedicarboximide (DBPI) molecules, mixed with polymethyl methacrylate (PMMA) and stearic acid (SA). J- aggregates of DBPI molecules in the mixed LB films have been confirmed by UV-Vis absorption spectroscopic study. Formation of organized structure of molecular stacking in the mixed LB films gives rise to the strong excimeric emission, which is manifested by a broad structureless band in the longer wavelength region of the fluorescence spectra and is confirmed by excitation spectroscopic study. A weak hump at around 576 nm due to monomeric emission is observed in the fluorescence spectra of 0.1 M of DBPI-PMMA mixed LB films of lower number of layers. The intensity of the 0-0 band at 530 nm in the fluorescence spectra is observed to be a function of the molefraction, number of layers, surface pressure of lifting and the matrix materials.     

High performance polymer light-emitting diodes doped with a novel phosphorescent iridium complex

High performance polymer light-emitting diodes (PLEDs) based on a phosphor of noble metal complex bis(1,2-dipheny1-1H-benzoimidazole) iridium (acetylacetonate) [(pbi)₂Ir(acac)] doped in poly(N-vinylcarbazole) (PVK) host with various concentration were demonstrated. The photoluminescence (PL) and electroluminescence (EL) spectra of the PLEDs exhibited an emission intensity decrease of PVK and a gradually enhanced feature of (pbi)₂Ir(acac) with increased doping concentration. The device with a 5 wt% (pbi)₂Ir(acac) doped PVK system showed a high power efficiency of 3.84 lm/W and a luminance of 26,006 cd/m². The results indicated that both energy transfer and charge trapping have a significant influence on the performance of PLEDs. The devices have a broadened EL spectrum of full-width at half-maximum (FWHM) more than 100 nm, which can be realized for WOLEDs.     

Photoluminescence and electroluminescence of a novel green-yellow emitting material-5,6-Bis-[4-(naphthalene-1-yl-phenyl-amino)-phenyl]-pyrazine-2,3-dicarbonitrile

A new compound with intramolecular charge transfer (ICT) property—5,6-Bis-[4-(naphthalene-1-yl-phenyl-amino)-phenyl]-pyrazine-2,3-dicarbonitrile(BNPPDC) was synthesized. The new compound was strongly fluorescent in non-polar and moderately polar solvents, as well as in thin solid film. The absorption and emission maxima shifted to longer wavelength with increasing solvent polarity. The fluorescence quantum yield also increased with increasing solvent polarity from non-polar to moderately polar solvents, then decreased with further increase of solvent polarity. This indicates both “positive” and “negative” solvatokinetic effects co-existed. Using this material as hole-transporting emitter and host emitter, we fabricated two electroluminescent (EL) devices with structures of A (ITO/BNPPDC (45 nm)/1,3,5-tris(N-phenylbenzimidazol-2-yl)benzene (TPBI) (45 nm)/Mg:Ag (200 nm) and B (ITO/N,N′-diphenyl-N,N′-bis-(3-methylphenyl) (1,1′-diphenyl)4,4′-diamine (TPD) (50 nm)/BNPPDC (20 nm)/1,3,5-tris(N-phenylbenzimidazol-2-yl)benzene (TPBI) (45 nm)/Mg:Ag (200 nm). The devices showed green-yellow EL emission with good efficiency and high brightness. For example, the device A exhibited a high brightness of 17400 cd/m² at a driving voltage of 11 V and a very low turn-on voltage (2.9 V), as well as a maximum luminous efficiency 3.61 cd/A. The device B showed a similar performance with a high brightness of 12650 cd/m² at a driving voltage of 13 V and a maximum luminous efficiency 3.62 cd/A. In addition, the EL devices using BNPPDC as a host and 4-(dicyanomethylene)-2-t-butyl-6-(1,1,7,7-tetramethyljulolidyl-9-enyl)-4H-pyran (DCJTB) as a dopant (configuration: ITO/TPD (60 nm)/BNPPDC:DCJTB (2%) (30 nm)/TPBI (35 nm)/Mg:Ag (200 nm)) showed a good performance with a brightness of 150 cd/m² at 4.5 V, a maximum brightness of 12600 cd/m² at 11.5 V, and a maximum luminous efficiency of 3.30 cd/A.     

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.     

pH dependent interaction of biofunctionalized CdS nanoparticles with nucleobases and nucleotides: A fluorimetric study

The interaction of DNA bases and corresponding nucleotides with CdS nanoparticles (NPs), biofunctionalized by cysteine, has been investigated by absorption and fluorescence spectroscopy. Unique enhancement effect of adenine, in contrast to other nucleobases, on the luminescence of cysteine capped CdS (cys-CdS) NPs at both pH 7.5 and 10.5 was found, the extent of enhancement being much higher at pH 10.5. At the latter pH, the difference optical absorption spectra show development of new peak at 278 nm with corresponding decrease in the absorption of adenine at 260 nm, which is attributed to binding of adenine anion to the CdS surface through N7 of the purine ring. Appearance of a new band at 478 cm⁻¹ and concomitant shift in the C₈-N₇ vibrations to 1610 cm⁻¹ in the FTIR spectra of cys-CdS NPs with adenine also suggest Cd-N7 binding on the particle surface. Amongst various nucleotides, ATP exhibited maximum luminescence enhancement on CdS NPs for a given change in concentration in the micro-molar range at physiological pH. A quantitative correlation between ATP concentration and PL enhancement of CdS NPs has been established, a step which in future might assist in developing new protocols for fluorescence sensing of adenine nucleotides under certain pathological conditions.     

Fluorometric determination of proteins using the terbium (III)-2-thenoyltrifluoroacetone-sodium dodecyl benzene sulfonate-protein system

It is found that in hexamethylene tetramine (HMTA)-HCl buffer of pH=8.00, proteins can enhance the fluorescence of terbium (III) (Tb³⁺)-2-thenoyltrifluoroacetone (TTA)-sodium dodecyl benzene sulfonate (SDBS) system. Based on this, a sensitive method for the determination of proteins is proposed. The experiments indicate that under the optimum conditions, the enhanced fluorescence intensity is in proportion to the concentration of proteins in the range of 4.0×10⁻⁹-7.5×10⁻⁶ g/mL for bovine serum albumin (BSA), 5.0×10⁻⁹-1.5×10⁻⁵ g/mL for human serum albumin (HSA), 1.0×10⁻⁸-7.5×10⁻⁶ g/mL for egg albumin (EA). Their detection limits (S/N=3) are 0.5, 0.8 and 2.0 ng/mL, respectively. The interaction mechanism is also studied.     

Optical characterization of CdS semiconductor nanoparticles capped with starch

Starch capped cadmium sulfide (CdS) nanoparticles were synthesized by aqueous solution precipitation. Starch added during the synthesis of nanoparticles resulted in cadmium-rich nanoparticles forming a stable complex with starch. The size of the CdS quantum dots was measured using high resolution transmission electron microscopy (HRTEM) and X-ray diffraction (XRD). The average diameter (d) of nanoparticles spanned the range 4.8 ± 0.4 to 5.7 ± 0.2 nm when the pH of the solution was varied within the range 10-14. The main Raman phonon of CdS, the longitudinal optical mode located around 300 cm⁻¹, softens as diameter decreases, in accordance with theoretical predictions. In addition, the largest Raman response of starch, near 478 cm⁻¹, related with the important skeletal vibration modes of the starch pyranose ring, dominates the spectra of the CdS capped nanoparticles and also softens as the size decreases. This fact indicates a strain variation on CdS as a function of d which increases as the pH increases.     

Photosensitivity and grating development in trans-4-stilbenemethanol-doped poly(methyl methacrylate) materials

This paper reports the photosensitivity of poly(methyl methacrylate) (PMMA) and its copolymer doped with trans-4-stilbenemethanol. UV irradiation of the doped-PMMA at 325 nm induced the trans- to cis-isomerization of the dopant. This process was confirmed by ¹H NMR spectra of trans-4-stilbenemethanol in CDCL₃ solvent before and after irradiation. The isomerization can be initiated by the irradiation with an intensity of 0.62 mW/cm². Photo-induced refractive index change of −0.0024 was obtained when a PMMA copolymer film doped with 5.1 wt% dopant was exposed to 325 nm light. Lorentz-Lorenz equation was used to estimate the refractive index of a trans-4-stilbenemethanol-PMMA composite and a trans-4-stilbenemethanol-PMMA copolymer composite from the mole refraction and van der Waals volume of each component. A slight elevation of molecular packing coefficient (K) for PMMA and its copolymer containing the dopant implies a denser aggregation as compared to the polymer without the dopant. Long period gratings were created in doped-PMMA films and doped-PMMA copolymer fibers using amplitude mask technique. Gratings were confirmed by microscopic observation and diffraction patterns.     

Photoluminescence of Si from Si nanocrystal-doped SiO2/Si multilayered sample

A multilayered Si nanocrystal-doped SiO₂/Si (or Si-nc:SiO₂/Si) sample structure is studied to acquire strong photoluminescence (PL) emission of Si via modulating excess Si concentration. The Si-nc:SiO₂ results from SiO thin film after thermal annealing. The total thickness of SiO layer remains 150 nm, and is partitioned equally into a number of sublayers (N = 3, 5, 10, or 30) by Si interlayers. For each N-layered sample, a maximal PL intensity of Si can be obtained via optimizing the thickness of Si interlayer (or d_Si). This maximal PL intensity varies with N, but the ratio of Si to O is nearly a constant. The brightest sample is found to be that of N = 10 and d_Si = 1 nm, whose PL intensity is ∼5 times that of N = 1 without additional Si doping, and ∼2.5 times that of Si-nc:SiO₂ prepared by co-evaporating of SiO and Si at the same optimized ratio of Si to O. Discussions are made based on PL, TEM, EDX and reflectance measurements.     

Optical properties and electric conductivity of gold nanoparticle-containing, hydrogel-based thin layer composite films obtained by photopolymerization

Poly(acrylamide) [poly(AAm)] and poly(N-isopropyl-acrylamide) [poly(NIPAAm)] based gel films containing Au nanoparticles (d = 14 ± 2.5 nm) were synthesized. Monomers and cross-linker were added to a gold nanodispersion, and after the addition of the initiator, polymer films were prepared on the surface of an interdigital microelectrode by photopolymerization. In the course of the syntheses the gold concentration of the films was constant (10.8 μg/cm²) and the volume fraction of Au nanoparticles (?_Au) in the polymer gel films varied in the range of 0.58-85.3%. Poly(AAm)-based films swell when the temperature increases: due to a temperature shift of 15 °C the Au plasmon absorption maximum at λ = ∼532 nm was shifted towards shorter wavelengths by 16.6 nm (blue shift) through the swelling of the polymer gel film. In the case of poly(NIPAAm) the temperature-induced shrinking resulted in a red shift, namely the maximum was shifted by 18.07 nm by a temperature shift of 15 °C. In the case of both composites, the electric conductivity of the samples was shown to increase with increasing Au particle concentration. In the case of the poly(AAm)-based composite containing ?_Au = 0.85 gold the resistance of the film spread on the surface of the electrode was 0.16 MΩ at 25 °C and 0.66 MΩ at 50 °C, i.e. the conductivity of the sample decreased with increasing temperature. The opposite effect is observed in the case of the poly(NIPAAm)-based composite: as temperature is raised, the resistance of the composite abruptly drops at the point of collapse of the NIPAAm gel (it is 0.28 MΩ at 32 °C and only 0.021 MΩ at 35 °C). This thermosensitive effect was detectable only at sufficiently high Au contents (?_Au = 0.85) in both gels.     

Synchronous fluorescence determination of ciprofloxacin in the pharmaceutical formulation and human serum based on the perturbed luminescence of rare-earth ions

A simple, rapid and sensitive synchronous fluorescence method was developed for the determination of ciprofloxacin (CPFX) in the pharmaceutical formulation and human serum. The results show that when Y³⁺ is added into the CPFX solution, the characteristic fluorescence of Y³⁺ is not emitted whereas the fluorescence intensity of CPFX is significantly enhanced. The synchronous fluorescence technology is employed in this method to directly determine trace amount of CPFX in human serum. A linear relationship between the fluorescence intensity and the CPFX concentration is obtained in the range of 1.0×10⁻⁹ ∼5.0×10⁻⁶ mol L⁻¹. The limit of detection (LOD) of this method attains as low as 2.0×10⁻¹⁰ mol L⁻¹ (S/N=3). The selectivity of this method is also very good. Common metal ions, rare-earth ions and some pharmaceuticals, which are usually used together with CPFX in the clinic, do not interfere with the determination of CPFX under general conditions.     

Low-voltage cathodoluminescence property of Li-doped Gd2−xYxO3:Eu

Cathodoluminescent (CL) spectra of Li-doped Gd_2−xY_xO₃:Eu³⁺ solid-solution (0.0?x?0.8) were investigated at low voltages (300 V-1 kV). The CL intensity is maximum for the composition of x=0.2 and gradually reduces with increasing the amount of substituted Y content. In particular, small (∼100 nm) particles of Li-doped Gd_1.8Y_0.2O₃:Eu³⁺ are obtained by firing the citrate precursors at only 650°C for 18 h. Relative red-emission intensity at 300 V of this phosphor is close to 180% in comparison with that of commercial red phosphor Y₂O₃:Eu³⁺. An increase of firing temperature to 900°C results in 400-600 nm sized spherical particles. At low voltages (300-800 V), the CL emission of 100 nm sized particles is much stronger than that of 400-600 nm sized ones. In contrast, the larger particles exhibit the higher CL emission intensity at high voltages (1-10 kV). Taking into consideration small spherical morphology and effective CL emission, Li-doped Gd_1.8Y_0.2O₃:Eu³⁺ appears to be an efficient phosphor material for low voltage field emission display.     

Study on the interaction of tropisetron hydrochloride and l-tryptophan by spectrofluorimetry and its analytical application

A new method to determine tropisetron hydrochloride with l-tryptophan in the medium with pH=9.0 was studied, which is based on the fluorescence quenching effect of tropisetron hydrochloride on l-tryptophan. The fluorescence quenching mechanism and various factors influencing fluorescence quenching were discussed. Under the optimum conditions, the linear range and detection limit were 0.03-12.0 and 0.01 μg/mL (correlation coefficient r=0.9970), respectively. The calibration curve equation was ΔF=6.17+12.56 C (μg/mL). RSD was 3.4% (c=4.0 μg/mL, n=5); the detection limit estimated (S/N=3) was 0.01 μg/mL. The proposed method had been successfully applied to determine tropisetron hydrochloride in real samples and the obtained results were in good agreement with the results of the official method.     

Photoluminescence of hexagonal boron nitride: Effect of surface oxidation under UV-laser irradiation

We report on the UV laser-induced fluorescence of hexagonal boron nitride (h-BN) following nanosecond laser irradiation under vacuum and in different environments of nitrogen gas and ambient air. The observed fluorescence bands are tentatively ascribed to impurity and mono (V_N) or multiple (m-V_N with m=2 or 3) nitrogen vacancies. A structured fluorescence band between 300 and 350 nm is assigned to impurity-band transition and its complex lineshape is attributed to phonon replicas. An additional band at 340 nm, assigned to V_N vacancies on surface, is observed under vacuum and quenched by adsorbed molecular oxygen. UV-irradiation of h-BN under vacuum results in a broad asymmetric fluorescence at ∼400 nm assigned to m-V_N vacancies; further irradiation breaks more B-N bonds enriching the surface with elemental boron. However, no boron deposit appears under irradiation of samples in ambient atmosphere. This effect is explained by oxygen healing of radiation-induced surface defects. Formation of the oxide layer prevents B-N dissociation and preserves the bulk sample stoichiometry.     

Effect of substrate temperature on the morphology, structural and optical properties of Zn1−xCoxO thin films

Zn_1−xCo_xO thin films with c-axis preferred orientation were deposited on sapphire (0 0 0 1) by pulsed laser deposition (PLD) technique at different substrate temperatures in an oxygen-deficient ambient. The effect of substrate temperature on the microstructure, morphology and the optical properties of the Zn_1−xCo_xO thin films was studied by means of X-ray diffraction (XRD), atomic force microscopy (AFM), UV-visible-NIR spectrophotometer, fluorescence spectrophotometer. The results showed that the crystallization of the films was promoted as substrate temperature rose. The structure of the samples was not distorted by the Co incorporating into ZnO lattice. The surface roughness of all samples decreased as substrate temperature increased. The Co concentration in the film was higher than in the target. Emission peak near band edge emission of ZnO from the PL spectra of the all samples was quenched because the dopant complexes acted as non-radiative centers. While three emission bands located at 409 nm (3.03 eV), 496 nm (2.5 eV) and 513 nm (2.4 eV) were, respectively, observed from the PL spectra of the four samples. The three emission bands were in relation to Zn interstitials, Zn vacancies and the complex of V_O and Zn_i (V_OZn_i). The quantity of the Zn interstitials maintained invariable basically, while the quantity of the V_OZn_i slightly decreased as substrate temperature increased.     

Fluorometric determination of proteins using the yttrium(III)-sodium lauryl sulfate-rutin-protein system

It is found that rutin can react with yttrium(III) (Y³⁺), and emits fluorescence of rutin. The intensity is greatly enhanced by proteins in the presence of sodium lauryl sulfate (SLS). Based on this, a new fluorimetric method of determination of proteins is developed. Under optimum conditions, the enhanced intensity of fluorescence is in proportion to the concentration of proteins in the range of 5.0×10⁻⁹-1.0×10⁻⁵ g/mL for bovine serum albumin (BSA), 3.0×10⁻⁸-1.0×10⁻⁵ g/mL for human serum albumin (HSA) and 1.0×10⁻⁷-2.0×10⁻⁵ g/mL for egg albumin (EA). Their detection limits (S/N=3) are 1.6×10⁻⁹, 9.8×10⁻⁹ and 2.1×10⁻⁸ g/mL, respectively. The interaction mechanism is also studied.     

In vitro study of magnetic nanoparticles as the implant for implant assisted magnetic drug targeting

Magnetic nanoparticle (MNP) seeds were studied in vitro for use as an implant in implant assisted-magnetic drug targeting (IA-MDT). The magnetite seeds were captured in a porous polymer, mimicking capillary tissue, with an external magnetic field (70 mT) and then used subsequently to capture magnetic drug carrier particles (MDCPs) (0.87 μm diameter) with the same magnetic field. The effects of the MNP seed diameter (10, 50 and 100 nm), MNP seed concentration (0.25-2.0 mg/mL), and fluid velocity (0.03-0.15 cm/s) on the capture efficiency (CE) of both the MNP seeds and the MDCPs were studied. The CE of the 10 nm MNP seeds was never more than 30%, while those of the 50 and 100 nm MNP seeds was always greater than 80% and in many cases exceeded 90%. Only the MNP seed concentration affected its CE. The 10 nm MNP seeds did not increase the MDCP CE over that obtained in the absence of the MNP seeds, while the 50 and 100 nm MNP seeds increased significantly, typically by more than a factor of two. The 50 and 100 nm MNP seeds also exhibited similar abilities to capture the MDCPs, with the MDCP CE always increasing with decreasing fluid velocity and generally increasing with increasing MNP seed concentration. The MNP seed size, magnetic properties, and capacity to self-agglomerate and form clusters were key properties that make them a viable implant in IA-MDT.     

Planar quarter wave stacks prepared from chalcogenide Ge-Se and polymer polystyrene thin films

Planar quarter wave stacks based on amorphous chalcogenide Ge-Se alternating with polymer polystyrene (PS) thin films are reported as Bragg reflectors for near-infrared region. Chalcogenide films were prepared using a thermal evaporation (TE) while polymer films were deposited using a spin-coating technique. The film thicknesses, d∼165 nm for Ge₂₅Se₇₅ (n=2.35) and d∼250 nm for polymer film (n=1.53), were calculated to center the reflection band round 1550 nm, whose wavelengths are used in telecommunication. Optical properties of prepared multilayer stacks were determined in the range 400-2200 nm using spectral ellipsometry, optical transmission and reflection measurements. Total reflection for normal incidence of unpolarized light was observed from 1530 to 1740 nm for 8 Ge-Se+7 PS thin film stacks prepared on silicon wafer. In addition to total reflection of light with normal incidence, the omnidirectional total reflection of TE-polarized light from 8 Ge-Se+7 PS thin film stacks was observed. Reflection band maxima shifted with varying incident angles, i.e., 1420-1680 nm for 45° deflection from the normal and 1300-1630 nm for 70° deflection from the normal.     

One-step aqueous synthesis of CdS nanoparticles as a novel fluorescence probe for the ultrasensitive detection of DNA

One-step aqueous synthesis of CdS nanoparticles as a novel fluorescence probe for sensitive and selective determination of DNA with synchronous fluorescence spectrometric method has been developed. Different from the traditional organometallic route, in which toxic precursors or solvents might be used, the wet chemical approach demonstrated in this paper is superior in terms of simplicity, using of nontoxic materials, mild synthetic condition and good reproducibility. When Δλ=255 nm, maximum synchronous fluorescence is produced at 264 nm, the synchronous fluorescence intensity of the composite nanoparticles is significantly decreased in the presence of trace DNA at PH 0.91. Under optimal conditions, the linear ranges of the calibration curves are 0.08-30.0 μg mL⁻¹ for ctDNA and 0.05-35.0 μg mL⁻¹ for hsDNA, respectively. The detection limits are 1.5 ng mL⁻¹ for ctDNA and 2.2 ng mL⁻¹ for hsDNA, respectively. Furthermore, the method is successfully applied to the quantification of DNA in synthetic samples. The results show that this proposed method is stable, sensitive and practical for the determination of trace DNA.     

Determination of the positron diffusion length in Kapton by analysing the positronium emission

Doppler profile spectroscopy and Compton-to-peak ratio analysis have been used to study the positronium (Ps) emission from the Kapton surface as a function of the positron implantation energy E.Two different positions for the sample have been performed in the experiment.In the first case the sample and the Ge-detector are perpendicular to the positron beam. With this geometry the emission of para-positronium (p-Ps) is detected as a narrow central peak.In the second case, by rotating the sample 45° with respect to the beam axis, the emission of p-Ps is detected as a blue-shifted fly away peak. The implantation of the positrons is described by the Makhov profile, where we used the modified median implantation for polymers as given by Algers et al. [J. Algers, P. Sperr, W. Egger, G. Kögel, F.H.J. Maurer, Phys. Rev. B 67 (2003) 125404].Thermalised positrons can diffuse to the surface and may pick up an electron to be emitted as Ps. We found a thermal and or epithermal positron diffusion length L₊ = 5.43 ± 0.71 nm and L₊ = 5.51 ± 0.28 nm correspondingly for both cases, which is much more than the one found by Brusa et al. [R.S. Brusa, A. Dupasquier, E. Galvanetto, A. Zecca, Appl. Phys. A 54 (1992) 233]. The respective efficiency for the emission of Ps by picking up an electron from the surface is found to be f_pu = 0.247 ± 0.012 and f_pu = 0.156 ± 0.003.