Radiative quantum efficiency of CdSe/ZnS core-shell colloidal solutions: Size-dependence

Thermo-optical parameters of CdSe/ZnS core-shell nanoparticles suspended in toluene were measured using a thermal lens (TL) technique. TL transient measurements were performed using the mode-mismatched dual-beam (excitation and probe) configuration. A He-Ne laser at λ_p = 632.8 nm was used as the probe beam and an Ar⁺ laser (at λ_e = 514.5 nm) was used as the excitation beam for studies as a function of both core size and concentration of CdSe/ZnS nanocrystals. The fraction thermal load (φ) and radiative quantum efficiencies (η) of the CdSe/ZnS were determined. Dependence on core size (∼2-5 nm) and concentration (∼0.01-0.62 mg/ml) was observed for both φ and η parameters.     

Photoluminescence spectra of thin films containing CdSe/ZnS quantum dots irradiated by 532-nm laser radiation and gamma-rays

We have investigated temporal behavior of the photoluminescence (PL) spectra of thin films containing CdSe/ZnS quantum dots irradiated by 532 nm laser radiation and gamma-rays. Under ∼100 W/cm² laser radiation, the PL intensity (I_PL) increases with irradiation time upto about 500 s and thereafter declines linearly. The wavelength of the PL emission (λ_peak) exhibits a blue-shift with exposure time. Upon simultaneous irradiation by 100 W/cm² 532-nm laser, as well as 0.57 and 1.06 MeV gamma-rays, the temporal behaviors of both I_PL and λ_peak are significantly different; I_PL increases to a saturation level, and the magnitude of the blue-shift in λ_peak is reduced. We discuss possible mechanisms underlying these results.     

Intermediate intensity levels during the emission intermittency of single CdSe/ZnS quantum dots

We report on an intermediate intensity level in the emission intermittency of single CdSe/ZnS core shell quantum dots, which has been overlooked in previous experiments most likely due to its low quantum efficiency. The intermediate intensity level is observed in CdSe/ZnS quantum dots of large diameter (about 5 nm diameter) and appears to be independent of the general dark state power law dynamics. The dim emission periods are found to be exponentially distributed and thus correspond to similar findings in CdSe/CdS quantum dots, where their existence has been interpreted in terms of the emission of a positively charged trion.     

Thermal decomposition of toluene: Overall rate and branching ratio

The two-channel thermal decomposition of toluene, C₆H₅CH₃ → C₆H₅CH₂ + H (1) and C₆H₅CH₃ → C₆H₅ + CH₃ (2), was investigated in shock tube experiments over the temperature range of 1400-1780 K at a pressure of 1.5 (±0.1) bar. Rate coefficients for reactions (1) and (2) were determined by monitoring benzyl radical (C₆H₅CH₂) absorption at 266 nm during the decomposition of toluene diluted in argon and modeling the temporal behavior of the benzyl concentration with a kinetic model. The first-order rate coefficients determined at a pressure of 1.5 bar are expressed by k₁(T) = 2.09 × 10¹⁵ exp (−87510 [cal/mol]/RT) [s⁻¹] and k₂(T) = 2.66 × 10¹⁶ exp (−97880 [cal/mol]/RT) [s⁻¹]. The resulting branching ratio, k₁/(k₁ + k₂), ranges from 0.8 at 1350 K to 0.6 at 1800 K.     

Probabilistically perfect quantum cloning and unambiguous state discrimination

We consider the N → M probabilistically perfect quantum cloning machine that perfectly produces M faithful copies from N identical input states, where the input states are selected, with prior probabilities η₁and η₂ = 1 − η₁, from a given set of the two linearly independent states |ψ₁〉^⊗ N = (cosθ|0〉 + sinθ|1〉)^⊗ N and |ψ₂〉^⊗ N = (sinθ|0〉 + cosθ|1〉)^⊗ N (θ∈(0,π/2)). We derive the optimal distribution of the success probabilities. When M approaches infinite, the probabilistically perfect quantum cloning can be regarded as a kind of the unambiguous state discrimination, and theoretically provides the upper bound of the unambiguous state discrimination. By using the optimal distribution of the success probabilities of the optimal asymmetric 1 → M probabilistically perfect quantum cloning, we can derive the maximum average success probability of the unambiguous discrimination of two nonorthogonal quantum states |ψ₁〉and|ψ₂〉. As an example, we give the explicit transformation of the optimal symmetric 1 → M probabilistically perfect quantum cloning to copy the two input states |ψ₁〉 and |ψ₂〉.     

Microstructuring of fused silica by laser-induced backside wet etching using picosecond laser pulses

The laser-induced backside wet etching (LIBWE) is an advanced laser processing method used for structuring transparent materials. LIBWE with nanosecond laser pulses has been successfully demonstrated for various materials, e.g. oxides (fused silica, sapphire) or fluorides (CaF₂, MgF₂), and applied for the fabrication of microstructures. In the present study, LIBWE of fused silica with mode-locked picosecond (t_p = 10 ps) lasers at UV wavelengths (λ₁ = 355 nm and λ₂ = 266 nm) using a (pyrene) toluene solution was demonstrated for the first time. The influence of the experimental parameters, such as laser fluence, pulse number, and absorbing liquid, on the etch rate and the resulting surface morphology were investigated. The etch rate grew linearly with the laser fluence in the low and in the high fluence range with different slopes. Incubation at low pulse numbers as well as a nearly constant etch rate after a specific pulse number for example were observed. Additionally, the etch rate depended on the absorbing liquid used; whereas the higher absorption of the admixture of pyrene in the used toluene enhances the etch rate and decreases the threshold fluence. With a λ₁ = 266 nm laser set-up, an exceptionally smooth surface in the etch pits was achieved. For both wavelengths (λ₁ = 266 nm and λ₂ = 355 nm), LIPSS (laser-induced periodic surface structures) formation was observed, especially at laser fluences near the thresholds of 170 and 120 mJ/cm², respectively.     

Investigations on structural and optical properties of Zn1−xGdxS nanoparticles

Zn_1−xGd_xS (x = 0.00, 0.02 and 0.04) nanoparticles were synthesized by facile chemical co-precipitation method using PVP as a surfactant. ZnS nanoparticles could be doped with Gd ions during synthesis without altering the XRD patterns of ZnS. Also, the pattern of the powders showed cubic zincblende structure. The particle size obtained from the XRD studies lies in the range 3-5 nm, whereas from TEM analysis it is 4 nm for x = 0.02 sample. The UV-Vis absorption spectra revealed that Zn_1−xGd_xS nanoparticles exhibit strong confinement effect as the blue shift in the absorption spectra with that of the undoped ZnS. The photoluminescence spectra showed enhanced luminescence intensity and the entry of Gd into host lattice.     

Synthesis and investigation of nonlinear optical properties of semiconductor ZnS nanoparticles

ZnS nanoparticles were prepared by a simple chemical method and using PVP (poly vinylpyrrolidone) as capping agent. The sample was characterized by UV-vis spectrophotometer, X-ray diffraction (XRD) and Z-scan technique. XRD pattern showed that the ZnS nanoparticles had zinc blende structure with an average size of about 2.18 nm. The value of band gap of these nanoparticles was measured to be 4.20 eV. The nonlinear optical properties of ZnS nanoparticles in aqueous solution were studied by Z-scan technique using CW He-Ne laser at 632.8 nm. The nonlinear absorption coefficient (β) was estimated to be as high as 3.2×10⁻³ cm/W and the nonlinear refractive index (n₂) was in order of 10⁻⁸ cm²/W. The sign of the nonlinear refractive index obtained negative that indicated this material exhibits self-defocusing optical nonlinearity.     

Size controlled synthesis of semiconductor nanocrystals in a continuous-flow mode microcapillary reactor

A microcapillary reactor with 320 μm inner diameter was utilized for CdSe nanoparticle synthesis. The influence of the reaction temperature and flow rate of precursors on the size and size distribution of prepared CdSe nanoparticles was systematically studied. The as-prepared nanoparticles exhibit sharp excitonic absorption and photoluminescence peak (FWHM 30 nm) with a quantum-yield around 10–40%. The microcapillary reactor was also used for CdSe/ZnS core-shell nanoparticle synthesis in continuous-flow mode. The quantum yield of the core-shell nanoparticles was found to be considerably influenced by the reactor temperature and have a close correlation with the thickness of ZnS shell under growth. An optimized quantum yield up to 70% was obtained for the CdSe/ZnS core-shell nanoparticles.     

Magnetic properties of Mn-oxide nanoparticles dispersed in an amorphous SiO2 matrix

Samples of Mn-oxide nanoparticles dispersed in an amorphous SiO₂ matrix with manganese concentration 0.7 and 3 at% have been synthesized by a sol-gel method. Transmission electron microscopy analysis has shown that the samples contain agglomerates of amorphous silica particles 10-20 nm in size. In silica matrix two types of Mn-rich particles are dispersed, smaller nanoparticles with dimensions between 3 and 10 nm, and larger crystalline areas consisting of aggregates of the smaller nanoparticles. High-temperature magnetic susceptibility study reveals that dominant magnetic phase at higher temperatures is λ-MnO₂. At temperatures below T_C=43 K strong ferrimagnetism originating from the minor Mn₃O₄ phase masks the relatively weak magnetism of λ-MnO₂ with antiferromagnetic interactions. Magnetic field dependence of the maximum in the zero-field-cooled magnetization for both the samples in the vicinity of 40 K, and a frequency shift of the real component of the ac magnetic susceptibility in the sample with 3 at% Mn suggest that the magnetic moments of the smaller Mn₃O₄ nanoparticles with dimensions below 10 nm are exposed to thermally activated blocking process just below the Curie temperature T_C. Appearance of a maximum in the zero-field-cooled magnetization for both the samples below 10 K indicates possible spin glass freezing of the magnetic moments at low temperatures which might occur in the geometrically frustrated Mn sublattice of the λ-MnO₂ crystal structure.     

Synthesis and photoluminescent and nonlinear optical properties of manganese doped ZnS nanoparticles

In this work we synthesized ZnS:Mn²⁺ nanoparticles by chemical method using PVP (polyvinylpyrrolidone) as a capping agent in aqueous solution. The structure and optical properties of the resultant product were characterized using UV-vis optical spectroscopy, X-ray diffraction (XRD), photoluminescence (PL) and z-scan techniques. UV-vis spectra for all samples showed an excitonic peak at around 292 nm, indicating that concentration of Mn²⁺ ions does not alter the band gap of nanoparticles. XRD patterns showed that the ZnS:Mn²⁺ nanoparticles have zinc blende structure with the average crystalline sizes of about 2 nm. The room temperature photoluminescence (PL) spectrum of ZnS:Mn²⁺ exhibited an orange-red emission at 594 nm due to the ⁴T₁-⁶A₁ transition in Mn²⁺. The PL intensity increased with increase in the Mn²⁺ ion concentration. The second-order nonlinear optical properties of nanoparticles were studied using a continuous-wave (CW) He-Ne laser by z-scan technique. The nonlinear refractive indices of nanoparticles were in the order of 10⁻⁸ cm²/W with negative sign and the nonlinear absorption indices of these nanoparticles were obtained to be about 10⁻³ cm/W with positive sign.     

Specific features of luminescence quenching in a nematic liquid crystal doped with nanoparticles

The change in the intensity of the photoluminescence (PL) spectra of nematic liquid crystal (NLC) composites as a function of the concentration of CdSe/ZnS semiconductor quantum dots (QDs) and TiO₂ and ZrO₂ nanoparticles ~5 nm in diameter has been investigated. It is shown that the PL-quenching intensity in composites with CdSe/ZnS QDs exceeds that in composites with TiO₂ and ZrO₂ nanoparticles. The lowfrequency spectra of these composites with a concentration of 0.1 wt %, recorded in the range of 10²–10³ Hz, and the content of mobile ions in them have been investigated. It is found that the dielectric loss in the composite with CdSe/ZnS QDs is much higher and the content of mobile ions is larger by a factor of 3 than in the composites with TiO₂ and ZrO₂ nanoparticles. It is shown that an increase in the CdSe/ZnS QD concentration in NLC composites leads to an increase in the dielectric loss and a decrease in the PL intensity. Possible mechanisms of the interaction between NLC molecules and CdSe/ZnS QDs are discussed.     

On the formation and decomposition of C7H8

The kinetics of reactions on the C₇H₈ surface were studied with state-of-the-art ab initio transition state theory (TST) and master equation methodologies. A priori predictions of the capture rate for C₆H₅ + CH₃ and for C₇H₇ + H are obtained from direct variable reaction coordinate TST simulations. These simulations employ small basis set CASPT2 interaction energies coupled with one-dimensional reaction path corrections based on higher level simulations for related reactions. For the C₇H₇ + H reaction, predictions are obtained for both the total rate and for the branching between toluene, o-isotoluene and p-isotoluene. A mapping of the low energy pathways for isomerization from these three C₇H₈ isomers identifies a number of processes with barriers at or below the dissociation threshold. Nevertheless, at combustion temperatures the dissociation rates are predicted to exceed the isomerization rates, and it is reasonable to treat the kinetics of each isomer as a simple single well association/dissociation equilibrium. Master equation simulations yield predictions for the temperature and pressure dependence of each of the recombination and dissociation processes, as well as for the C₇H₇ + H → C₆H₅ + CH₃ bimolecular reaction. These simulations implement collisional energy transfer probabilities based on the work of Luther and co-workers. The theoretical predictions are found to be in satisfactory agreement with the available experimental data for the photodissociation of toluene, the temperature and pressure dependent dissociation of toluene, and the reaction of benzyl radical with H. For the C₆H₅ + CH₃ recombination, the theoretical predictions exceed the experimental measurements of Lin and coworkers by a factor of 2 or more for all temperatures.     

High power room-temperature design of terahertz quantum cascade laser based on difference frequency generation

Terahertz (THz) quantum cascade lasers (QCLs) are key elements for high-power terahertz beam generation for integrated applications. In this study, we design a highly nonlinear THz-QCL active region in order to increase the output power of the device especially at lower THz frequencies based on difference frequency generation (DFG) process. It has been shown that the output power increases for a 3.2 THz structure up to 1.2 μW at room temperature in comparison with the reported power of P = 0.3 μW in [1]. The mid-IR wavelengths associated with this laser are λ₁ = 12.12 μm and λ₂ = 13.93 μm, which are mixed in a medium with high second-order nonlinearity. A similar approach has been used to design an active region with THz frequency of 1.8 THz. The output power of this structure reaches to 1 μW at room temperature where the mid-IR wavelengths are λ₁ = 12.05 μm, λ₂ = 12.99 μm.     

Mechanoluminescence and thermoluminescence of Mn doped ZnS nanocrystals

This paper reports the synthesis of ZnS:Mn nanocrystals by the chemical route in which mercaptoethanol was used as the capping agent. The particle size of such nanocrystals was measured using XRD and TEM patterns and was found to be in between 3and 5 nm. It was found that the peak position of TL glow curve and the TL intensity of ZnS:Mn nanoparticles increases as the particle size is decreased. The isothermal decay technique is used to determine the trap-depth. The stability of the charge carriers in the traps increase with the decrease in size of the nanoparticles. The higher stability may be attributed to the higher surface/volume ratio and also to the increase in the trap-depth with decreasing particle size. When a ZnS:Mn nanocrystal is deformed the peak intensity I_m increases linearly with the increasing height of the load. After I_m, initially the ML intensity decreases at a fast rate, and later on it decreases at a slow rate. The ML in ZnS:Mn nanocrystals can be understood on the basis of the piezoelectrically induced electron detrapping model.     

Preparation of Ru-loaded CdS/Al-HMS nanocomposites and production of hydrogen by photocatalytic degradation of formic acid

The composite of aluminum-substituted mesoporous silica (Al-HMS) molecular sieve coupled with CdS (CdS/Al-HMS) was prepared by template, ion exchange and sulfurization reactions. The result of low angle XRD patterns showed that the low content of 2.5 wt% CdS is incorporated inside Al-HMS channels. The results of diffuse reflectance UV-visible spectra and fluorescence emission spectra exhibited that the absorption edge and photoluminescence peak for CdS/Al-HMS are blue-shifted about 75 nm and 40 nm in comparison to bulk CdS, respectively. The activities of hydrogen production by photocatalytic degradation of formic acid were evaluated under visible light irradiation (λ ≥ 420 nm) and the CdS/Al-HMS loaded 0.07 wt% Ru showed the highest H₂ evolution at a rate of 3.7 mL h⁻¹ with an apparent quantum yield of 1.2% at 420 nm.     

SrS:Ce/ZnS:Mn-A di-band phosphor for near-UV and blue LED-converted white-light emitting diodes

The SrS:Ce/ZnS:Mn phosphor blends with various combination viz 75:25, 50:50 and 25:75 were assign to generate the white-light emission using near-UV and blue-light emitting diodes (LED) as an excitation source. The SrS:Ce exhibits strong absorption at 427 nm and the corresponding intense emission occurs at 480 and 540 nm due to electron transition from 5d(²D)−4f(²F_5/2, _7/2) of Ce³⁺ ion as a result of spin-orbit coupling. The ZnS:Mn excited under same wavelength shows broad emission band with λ_max=582 nm originates due to 3d (⁴G−⁶S) level of Mn²⁺. Photoluminescence studies of phosphor blend excited using near-UV to blue light confirms the emitted radiation varies from cool to warm white light in the range 430-600 nm, applicable to LED lightings. The CIE chromaticity coordinate values measured using SrS:Ce/ZnS:Mn phosphor blend-coated 430 nm LED pumped phosphors in the ratio 75:25, 50:50 and 25:75 are found to be (0.235, 0.125), (0.280, 0.190) and (0.285, 0.250), respectively.     

Solvothermal synthesis and characterization of CdSe nanocrystals with controllable phase and morphology

Zinc blende (ZB) CdSe hollow nanospheres were solvothermally synthesized from the reaction of Cd(NO₃)₂·4H₂O with a homogeneously secondary Se source, which was first prepared by dissolving Se powder in the mixture of ethanol and oleic acid at 205 °C. As Se power directly reacted with Cd(NO₃)₂·4H₂O in the above mixed solvents, wurtzite (W) CdSe solid nanoparticles were produced. Time-dependent experiments suggested that the formation of CdSe hollow nanospheres was attributed to an inside-out Ostwald ripening process. The influences of reaction time, temperature and ethanol/oleic acid volume ratio on the morphology, phase and size of the hollow nanospheres were also studied. Infrared (IR) spectroscopy investigations revealed that oleic acid with long alkene chains behaved as a reducing agent to reduce Se powder to Se²⁻ in the synthesis. Photoluminescence (PL) measurements showed that the ZB CdSe hollow nanospheres presented an obvious blue-shifted emission by 42 nm, and the W CdSe solid nanoparticles exhibited a band gap emission of bulk counterpart.     

Optical properties of annealed Mn-doped ZnS nanoparticles

Cysteine stabilized ZnS and Mn²⁺-doped ZnS nanoparticles were synthesized by a wet chemical route. Using the ZnS:Mn²⁺ nanoparticles as seeds, silica-coated ZnS (ZnS@Si) and ZnS:Mn²⁺ (ZnS:Mn²⁺@Si) nanocomposites were formed in water by hydrolysis and condensation of tetramethoxyorthosilicate (TMOS). The influence of annealing in air, formier gas, and argon at 200-1000 °C on the chemical stability of ZnS@Si and ZnS:Mn²⁺@Si nanoparticles with and without silica shell was examined. Silica-coated nanoparticles showed an improved thermal stability over uncoated particles, which underwent a thermal combustion at 400 °C. The emission of the ZnS@Si and ZnS:Mn²⁺@Si passed through a minimum in photoluminescence intensity when annealed at 600 °C. Upon annealing at higher temperatures, ZnS@Si conserved the typical emission centered at 450 nm (blue). ZnS:Mn²⁺@Si yielded different high intensity emissions when heated to 800 °C depending on the gas employed. Emissions due to the Mn²⁺ at 530 nm (green; Zn₂SiO₄:Mn²⁺), 580 nm (orange; ZnS:Mn²⁺@Si), and 630 nm (red; ZnS:Mn²⁺@Si) were obtained. Therefore, with a single starting product a set of different colors was produced by adjusting the atmosphere wherein the powder is heated.     

The reaction of allyl radicals with oxygen atoms—rate coefficient and product branching

The primary product formation of the C₃H₅ + O reaction in the gas phase has been studied at room temperature. Allyl radicals (C₃H₅) and O atoms were generated by laser flash photolysis at λ = 193 nm of the precursors C₃H₅Cl, C₃H₅Br, C₆H₁₀ (1,5-hexadiene), and SO₂, respectively. The educts and the products were detected by using quantitative FTIR spectroscopy. The combined product analysis of the experiments with the different precursors leads to the following relative branching fractions: C₃H₅ + O → C₃H₄O + H (47%), C₂H₄ + H + CO (41%), H₂CO + C₂H₂ + H (7%), CH₃CCH + OH and CH₂CCH₂ + OH (<5%). The rate of reaction has been studied relative to CH₃OCH₂ + O and C₂H₅ + O in the temperature range from 300 to 623 K. Here, the radicals were produced via the fast reactions of propene, dimethyl ether, and ethane, respectively, with atomic fluorine. Laser-induced multiphoton ionization combined with TOF mass spectrometry and molecular beam sampling from a flow reactor was used for the specific and sensitive detection of the C₃H₅, C₂H₅, and CH₃COCH₂ radicals. The rate coefficient of the reaction C₃H₅ + O was derived with reference to the reaction C₂H₅ + O leading to k(C₃H₅ + O) = (1.11 ± 0.2) × 10¹⁴ cm³/(mol s) in the temperature range 300-623 K. The C₃H₅ + O rate and channel branching, when incorporated in a suitable detailed reaction mechanism, have a large influence on benzene and allyl concentration profiles in fuel-rich propene flames, on the propene flame speed, and on propene ignition delay times.