Understanding the role of particle size on photophysical properties of CdS:Eu nanocrystals

Here, we report the role of particle size on the photoluminescence (PL) properties of CdS:Eu³⁺ nanocrystals by steady-state and time-resolved PL spectroscopy. It is found that the average decay time 〈τ〉 of undoped CdS nanocrystals increases with increasing the size. The fast component (nanosecond) is assigned due to trapping and slow component (above 10 ns) is due to defect-related emission. The decrease of fast component from 6.6 to 1.32 ns and the slow component from 20 to 14.6 ns of CdS (host) is observed in presence of Eu ions, indicating that the energy transfer occurs from CdS nanoparticles to Eu³⁺ ions. The decay time of Eu³⁺ in CdS shows two decay components (microsecond scale) and we believe that the fast component is attributed to surface-bound Eu³⁺ ions and slow component is due to lattice-bound Eu³⁺ ions. Analysis suggests that PL efficiency of Eu³⁺ ions depends on size of nanoparticles.     

Influence of nanoenvironment on luminescence of Euactivated SnO2 nanocrystals

The emission intensity of the peak at 612 nm (⁵D₀→⁷F₂) of the Eu³⁺ ions activated SnO₂ nanocrystals (doped and coated) is found to be sensitive to the nanoenvironment. We have compared the luminescence efficiencies of the nanocrystals of SnO₂ doped by Eu₂O₃ with those of SnO₂ coated by Eu₂O₃ and we found that the intensities are significantly higher in coated nanocrystals. Furthermore, it is clear from luminescence intensity measurements that Eu³⁺ ions occupy low symmetry sites in the Eu₂O₃ coated SnO₂ nanocrystal. The analysis suggests that the radiative relaxation rate is higher in Eu₂O₃ coated SnO₂ nanocrystals than Eu₂O₃ doped SnO₂ nanocrystals due to the asymmetric environment of Eu³⁺ ions in coated samples.     

Excitonic polaron and phonon assisted photoluminescence of ZnO nanowires

The coupling strength of the radiative transition of hexagonal ZnO nanowires to the longitudinal optic (LO) phonon polarization field is deduced from temperature dependent photoluminescence spectra. An excitonic polaron formation is discussed to explain why the interaction of free excitons with LO phonons in ZnO nanowires is much stronger than that of bound excitons with LO phonons. The strong exciton-phonon coupling in ZnO nanowires affects not only the Haung-Ray S factor but also the FXA-1LO phonon energy spacing, which can be explained by the excitonic polaron formation.     

Luminescent CdSe and CdSe/CdS core-shell nanocrystals synthesized via a combination of solvothermal and two-phase thermal routes

A new solvothermal route has been developed for synthesizing the size-controlled CdSe nanocrystals with relatively narrow size distribution, and the photoluminescence (PL) quantum yields (QYs) of the nanocrystals can reach 5-10%. Then the obtained CdSe nanocrystals served as cores to prepare the core/shell CdSe/CdS nanocrystals via a two-phase thermal approach, which exhibited much higher PL QYs (up to 18-40%) than the CdSe core nanocrystals. The nanocrystal samples were characterized by ultraviolet-visible (UV-vis) absorption spectra, PL spectra, wide-angle X-ray diffraction (WAXD), X-ray photoelectron spectroscopy (XPS) and transmission electron microscopy (TEM).     

Luminescence of ZnO nanocrystals capped with an organic dye

ZnO nanocrystals capped with an organic dye Rhodamine 6G (Rh6G) were investigated by photoluminescence (PL) and cathodoluminescence (CL) techniques. PL and CL spectra showed a remarkable decrease in visible emission intensity after ZnO nanocrystals were capped with Rh6G, indicating that dangling bonds and defect states existing at the surface of ZnO nanocrystals were significantly passivated. Rh6G on the ZnO surface exhibited a monomer-like emission, and the intensity and the position of the emission were dependent on the dye concentration.     

Synthesis and optical properties of In-doped GaN nanocrystals

Indium-doped GaN nanocrystals with 5% and 10% In have been prepared by a low temperature solvothermal method using hexamethyldisilazane as the nitriding reagent. The nanocrystals show Raman bands at lower frequencies compared to GaN. Photoluminescence spectra of the In-doped GaN nanocrystals exhibit an increase in the FWHM with the decrease in the PL band energy, the band energy itself decreasing with increase in the In content.     

Photoluminescence properties of SiNx/Si amorphous multilayer structures grown by plasma-enhanced chemical vapor deposition

Very thin (nanometric) silicon layers were grown in between silicon nitride barriers by SiH₂Cl₂/H₂/NH₃ plasma-enhanced chemical vapor deposition (PECVD). The multilayer structures were deposited onto fused silica and silicon substrates. Deposition conditions were selected to favor Si cluster formation of different sizes in between the barriers of silicon nitride. The samples were thermally treated in an inert atmosphere for 1 h at 500 °C for dehydrogenation. Room-temperature photoluminescence (RT-PL) and optical transmission in different ranges were used to evaluate the optical properties of the structures. UV-VIS absorption spectra present two band edges. These band edges are well fitted by the Tauc model typically used for amorphous materials. RT-PL spectra are characterized by strong broad bands, which have a blue shift as a function of the deposition time of the silicon layer, even for as-grown samples. The broad luminescence could be associated with the confinement effect in the silicon clusters. After annealing of the samples, the PL bands red shift. This is probably due to the thermal decomposition of N-H bonds with further effusion of hydrogen and better nitrogen passivation of the nc-Si/SiN_x interfaces.     

Effect of annealing temperature on luminescence of Eu ions doped nanocrystal zirconia

Effect of annealing temperature on luminescence of Eu³⁺ ions was studied in nanocrystal zirconia prepared by co-precipitation. The XRDs reveal with annealing temperature increasing the tetragonal crystal phase of the samples is stable. The emission spectra show the strong emission at 595 and 604 nm at 394 nm excitation. Under continuous UV (394 nm) irradiation the 604 nm emission intensity changes of the samples show as a function of irradiation time. In addition, the charge-transfer states of the samples are affected by the annealing temperature. These are associated with the defects at/in the surface of the nanocrystalline ZrO₂ with Eu³⁺ ions.     

Investigation of spectroscopic properties and thermal stability of Er/Yb-co-doped Bi2O3-B2O3-Ga2O3 glasses

A series of Er³⁺/Yb³⁺-co-doped 60Bi₂O₃-(40−x) B₂O₃ -xGa₂O₃ (BBGA x=0, 4, 8, 12, 16 mol%) glasses have been prepared. The absorption spectra, emission spectra, fluorescence lifetime of Er³⁺:⁴I_13/2 level and thermal stability were measured and investigated. Three Judd-Ofelt intensity parameters Ω_t (t=2,4,6) (Ω₂=(4.67-5.93)×10⁻²⁰ cm², Ω₄=(1.50-1.81)×10⁻²⁰ cm², Ω₆=(0.92-1.17)×10⁻²⁰ cm²) of Er³⁺ ions were calculated by Judd-Ofelt theory. It is found that the Ω₆ first increases with the increase of Ga₂O₃ content from 0 to 8 mol% and then decreases, which is mainly affected by the number of non-bridging oxygen ions of the glass network. The high peak of stimulated emission cross-section () of Er³⁺: ⁴I_13/2→⁴I_15/2 transition were obtained according to McCumber theory and broad full width at half maximum (FWHM=69-76 nm) of the ⁴I_13/2→⁴I_15/2 transition of Er³⁺ ions were measured. The results indicate that these new BBGA glasses can be used as a candidate host material for potential broadband optical amplifiers.     

Concentration quenching in erbium-doped tellurite glasses

Er₂O₃-doped TeO₂-ZnO-La₂O₃ modified tellurite glasses were prepared by the conventional melt-quenching method, and the Er³⁺: ⁴I_13/2→⁴I_15/2 fluorescence properties have been studied for different Er³⁺ concentrations. Infrared spectra were measured in order to estimate the exact content of OH⁻ groups in samples. Based on the electric dipole-dipole interaction theory, the interaction parameter, C_Er,Er, for the migration rate of Er³⁺: ⁴I_13/2→⁴I_13/2 in modified tellurite glass was calculated. Finally, the concentration quenching mechanism using a model based on energy transfer and quenching by hydroxyl (OH⁻) groups was presented.     

Temperature-dependent photoluminescence of Mg-doped CdS nanowires

Sixfold symmetrical Mg-doped CdS nanowires have been fabricated through high temperature vapor-solid deposition process. The experimental study of the temperature-dependent photoluminescence properties of the Mg-doped CdS nanowires from 10 K to 300 K was reported. The Mg-doped CdS nanowires show intensive cyan-color light emission properties from 10 K to 200 K. The results indicate that there are two strong peaks situated at the green emission (at 528 nm) and red emission (at 655-695 nm), and two weak UV emission peaks at 378 nm and 417 nm, respectively. The ratio of green to red emission was decreased with temperature increased. When the temperature is above 200 K, the orange-color light was observed from the Mg-doped CdS nanowires. Therefore, the intensive emission properties of the Mg-doped CdS nanowires have a great potential for use as nanoscaled optoelectronic intensive light emitters under different temperature.     

Optical and structural properties of nanosized ZnGa2O4:Cr phosphor

Nanosized ZnGa₂O₄:Cr³⁺ powder is synthesized through hydrothermal method. The average particle size is 20 nm and they are spherical in shape. The excitation band from the charge transfer between Cr³⁺-O²⁻ shows a blueshift behavior due to quantum confinement effect. X-ray diffraction pattern, Fourier transform-infrared spectrum, and electron paramagnetic resonance signal indicate that nanosized ZnGa₂O₄:Cr³⁺ phosphor shows many defect-related energy states and heavy lattice distortion in comparison with bulk ZnGa₂O₄:Cr³⁺ phosphor. Many defect states result in more nonradiative loss and shorter decay time.     

Photoluminescence of YVO4:Tm phosphor prepared by a polymerizable complex method

This paper reports the photoluminescence (PL) properties of nanocrystalline YVO₄: Tm phosphor synthesized by the polymerizable complex method based on the Pechini-type reaction. The powder was characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), absorption spectroscopy and PL. The results of XRD and TEM show that, high-quality nanopowders with controlled morphology and microstructure were prepared at a relatively low temperature about 700 °C. Upon ultra violet excitation the vanadate host transferred energy to thulium ions efficiently and strong blue emission (475 nm) assigned to ¹G₄→³H₆ transmission is observed. By analyzing excitation and emission spectra of thulium doped yttrium vanadate, we deduced the mechanism of the energy transfer between vanadate host and thulium ions.     

Well-aligned ZnO nanocolumns grown by reactive electron beam evaporation

We report on the reactive electron beam evaporative growth of well-aligned ZnO nanocolumns on Si (001) wafers in the environment of NH₃/H₂ gas mixture by using polycrystalline ZnO ceramic target as source material. The growth was carried out at low temperatures (400-450 °C) without employing any metal catalysts. Field emission scanning electron microscopy (FESEM) revealed that nanocolumns with uniform distributions in their diameters, lengths, and densities were grown vertically from the substrates and terminated by smooth hexagonal (0001) facets with no terrace-like steps emerged, which should render potential applications such as inherent resonance cavities in fabricating ultraviolet-laser arrays. X-ray diffraction measurements revealed that ZnO nanocolumns were highly c-axis oriented, which is well consistent with the FESEM observations. More importantly, photoluminescence investigations of the nanocolumns demonstrated the strong excitonic emission and extremely weak deep level emission, indicating the high crystalloid and optical quality of the nanocolumns.     

Anomalous optical transitions in AlInGaN/GaN heterostructures grown by metalorganic chemical vapor deposition

Using temperature-dependent photoluminescence (PL) measurements, we report a comprehensive study on optical transitions in Al_yIn_xGa_1−x−yN epilayer with target composition, x=0.01 and y=0.07 and varying epilayer thickness of 40, 65 and 100 nm. In these quaternary alloys, we have observed an anomalous PL temperature dependence such as an S-shape band-edge PL peak shift and a W-shape spectral broadening with an increase in temperature. With an increase in excitation power density, the emission peak from the AlInGaN epilayers shows a blue shift at 100 K and a substantial red shift at room temperature. This is attributed to the localization of excitons at the band-tail states at low temperature. Compared to 40 and 65 nm thick epilayers, the initial blue shift observed with low excitation power from 100 nm thick AlInGaN epilayer at room temperature is caused by the existence of deeper localized states due to confinement effects arising from higher In and Al incorporation. The subsequent red shift of the PL peak can be attributed by free motion of delocalized carriers that leads to bandgap renormalization by screening. Due to competing effects of exciton and free carrier recombination processes, such behavior of optical transitions leads to two different values of exponent ‘k’ in the fitting of PL emission intensity as a function of excitation power.     

Structural, optical and electrical properties of Al-N codoped ZnO films by RF-assisted MOCVD method

N-doped ZnO films were produced using N₂ as N source by metal-organic chemical vapor deposition (MOCVD) system which has been improved with radio-frequency (RF)-assisted equipments. The data of secondary ion mass spectroscopy (SIMS) indicate that the concentration of N in N-doped ZnO films is around 5 × 10²⁰ cm⁻³, implying that sufficient incorporation of N into ZnO can be obtained by RF-assisted equipment. On this basis, the structural, optical and electrical properties of Al-N codoped ZnO films were studied. Then, the effect of RF power on crystal quality, surface morphologies, optical properties was analyzed using X-ray diffraction, atomic force microscopy and photo-luminescence methods. The results illustrate that the RF plasma is the key factor for the improvement of crystal quality. Then the observation of A⁰X recombination associated with N_O acceptor in low-temperature PL spectrum proved that some N atoms have occupied the positions of O atoms in ZnO films. Hall measurements shown that p-type ZnO film deposited on quartz glasses was obtained when RF power was 150 W for the Al-N codoped ZnO films, while the resistivity of N-doped ZnO films was rather high. Compared with the Al-doped ZnO film, the obviously increased resistivity of codoped films indicates that the formation of N_O acceptors compensate some donors in ZnO films effectively.     

The optical properties of the blends of CdSe nanocrystals and poly(N-vinylcarbazole)

The CdSe nanocrystals with different sizes were synthesized in aqueous solution through water-sol method using l-cysteine hydrochloride as the stabilizer. The pH-dependent optical properties of the CdSe nanocrystals were investigated. Furthermore, the CdSe nanocrystals were dispersed into chloroform by using a cationic surfactant, and mixed with poly(N-vinylcarbazole) (PVK) in different mass ratios. The investigation of the photoluminescence (PL) and absorption spectra of the CdSe:PVK blends suggested that energy transfer from the PVK excited states to the CdSe nanocrystals, and it is more efficient for the smaller size nanocrystals. In the meantime, it was found that the relative emission intensity of the CdSe nanocrystals to PVK in the blends depended on the mass ratios, and the emission from the CdSe nanocrystals was the strongest as the mass ratio of CdSe to PVK was 2:1.     

Lattice parameter and luminescence properties of europium activated yttrium oxide

Samples of yttrium oxide doped with trivalent europium have been prepared by ceramic techniques, under different synthesis conditions; barium chloride (BaCl₂) and sodium tetraborate (Na₂B₄O₇) were tested as flux. The improvement of luminescence properties in dependence on substitution of Eu³⁺ for Y³⁺ in the host lattice, under electron and UV excitations is demonstrated. The lattice parameter as a quantitative assessment of activator incorporation degree is proposed. The obtained results are discussed with respect to the employed processing method.     

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.     

Microstructure and multiphoton luminescence of Au nanocrystals prepared by using glancing deposition method

Au crystal columns embedded in SiO₂ with an average length of 480 nm and diameter of 30 nm were prepared by radio frequency co-sputtering technique with glancing angle. The photoluminescence (PL) of the Au-SiO₂ crystal column film exhibited polarization characteristic. With an increase of the laser power, the slope ∂ log(PL intensity)/∂ log(laser power) changed from 2 to 3, which indicated that the PL of Au-SiO₂ crystal columns were induced by two- and three-photon absorption, respectively.