Synthesis of high quality and monodisperse CdS:Mn/ZnS and CdS:Mn/CdS core–shell nanoparticles

CdS:Mn²⁺/ZnS and CdS:Mn²⁺/CdS core–shell nanoparticles were synthesized in aqueous medium via chemical precipitation method in an ambient atmosphere. Polyvinylpyrrolidone (PVP) was used as a capping agent. The effect of the shell (ZnS and CdS) thickness on CdS:Mn²⁺ nanoparticles was investigated. Inorganically passivated core/shell nanocrystals having a core (CdS:Mn²⁺) diameter of 4 nm and a ZnS-shell thickness of ∼0.5 nm exhibited improved PL intensity. Optimum concentration of doping ions (Mn²⁺) was selected through optical study. For all the core–shell samples two emission peaks were observed, the first one is band edge emission in the lower wavelength side due to energy transfer to the Mn²⁺ ions in the crystal lattice; the second emission is characteristic peak of Mn²⁺ ions (⁴T₁ → ⁶A₁). The XRD, TEM and PL results showed that the synthesized core–shell particles were of high quality and monodisperse.     

Quenching of Si nanocrystal photoluminescence by doping with gold or phosphorous

Si nanocrystals embedded in SiO₂ doped with P and Au at concentrations in the range of 1×10¹⁸-3×10²⁰ cm⁻³ exhibit photoluminescence quenching. Upon increasing the Au concentration, a gradual decrease in nanocrystal photoluminescence intensity is observed. Using a statistical model for luminescence quenching, we derive a typical radius of ∼3 nm for nanocrystals luminescing around 800 nm. Au doping also leads to a luminescence lifetime reduction, which is attributed to energy transfer between adjacent Si nanocrystals, possibly mediated by the presence of Au in the form of ions or nanocrystals. Doping with P at concentrations up to 3×10¹⁹ cm⁻³ leads to a luminescence enhancement, most likely due to passivation of the nanocrystal-SiO₂ interfaces. Upon further P doping the nanocrystal luminescence gradually decreases, with little change in luminescence lifetime.     

Temperature induced size selective synthesis of hybrid Cds/pepsin nanocrystals and their photoluminescence investigation

There is growing interest in materials chemistry for taking advantage of the physical and chemical properties of biomolecules in the development of next generation nanoscale materials for opto-electronic applications. A biomimetic approach to materials synthesis offers the possibility of controlling size, shape, crystal structure, orientation, and organization. The great progress has been made in the control that can be exerted over optical materials synthesis using biomolecules (protein, nucleic acid)/mineral interfaces as templates for directed synthesis. We have synthesized the CdS nanocrystals using pepsin by biomimetic technique at four different set temperatures. X-ray diffraction (XRD) and small angle X-ray scattering (SAXS) results showed that we are able to tune the size and distribution profile just by tuning the reaction (Rx) temperature and goes towards excitonic Bhor radius (2.5 nm) at low temperature (4 °C). The narrow absorption peak at 260 nm from Cd²⁺-pepsin complex dominates and indicates the size dispersion of the modified CdS nanoparticles are fairly monodisperse. Effective mass approximation (EMA) shows large blue-shift (~1 eV) in the band gap for the cubic phase from bulk hexagonal CdS. The photoluminescence (PL) and photoluminescence excitation (PLE) spectra are dominated by a strong and narrow band-edge emission tunable in the blue region indicating a narrow size distribution. The reduction in PL efficiency is observed when the Rx temperature increases however no change in PLE spectra and temporal profiles of the band-edge PL is observed. At 4 °C, high emission efficiency with shift of PL spectrum in the violet region is observed for 1.7 nm size CdS quantum dots (QDs). Presence of pepsin has slowed the PL decay which is of the order of 100 μs.     

Evidence for fast decay dynamics of the photoluminescence from Ge nanocrystals embedded in SiO2

We have investigated the origin of room temperature photoluminescence from ion-beam synthesized Ge nanocrystals (NCs) embedded in SiO₂ using steady state and time-resolved photoluminescence (PL) measurements. Ge NCs of diameter 4-13 nm were grown embedded in a thermally grown SiO₂ layer by Ge⁺ ion implantation and subsequent annealing. Steady state PL spectra show a peak at ∼2.1 eV originating from Ge NCs and another peak at ∼2.3 eV arising from ion-beam induced defects in the SiO₂ matrix. Time-resolved PL studies reveal double exponential decay dynamics on the nanoseconds time scale. The faster component of the decay with a time constant τ₁∼3.1 ns is attributed to the nonradiative lifetime, since the time constant reduces with increasing defect density. The slower component with time constant τ₂∼10 ns is attributed to radiative recombination at the Ge NCs. Our results are in close agreement with the theoretically predicted radiative lifetime for small Ge NCs.     

Preparation and characterization of CdS/Si coaxial nanowires

CdS/Si coaxial nanowires were fabricated via a simple one-step thermal evaporation of CdS powder in mass scale. Their crystallinities, general morphologies and detailed microstructures were characterized by using X-ray diffraction, scanning electron microscope, transmission electron microscope and Raman spectra. The CdS core crystallizes in a hexagonal wurtzite structure with lattice constants of a=0.4140 nm and c=0.6719 nm, and the Si shell is amorphous. Five Raman peaks from the CdS core were observed. They are 1LO at 305 cm⁻¹, 2LO at 601 cm⁻¹, A₁-TO at 212 cm⁻¹, E₁-TO at 234 cm⁻¹, and E₂ at 252 cm⁻¹. Photoluminescence measurements show that the nanowires have two emission bands around 510 and 590 nm, which originate from the intrinsic transitions of CdS cores and the amorphous Si shells, respectively.     

Synthesis and optical characterization of PVP and SHMP-encapsulated Mn-doped ZnS nanocrystals

Zinc sulfide semiconductor nanocrystals doped Mn²⁺ have been synthesized via a solution-based method utilizing optimum dopant concentration (4%) and employing polyvinyl pyrrolidone (PVP) and sodium hexametapolyphosphate (SHMP) as capping agents. UV-vis absorbance spectra for all of the synthesized nanocrystals show an exitonic peak at around 310 nm. The particle size and morphology were characterized by scanning electron microscopy (SEM), FT-IR, X-ray diffraction (XRD), transmission electron microscopy (TEM) and photoluminescence spectrum (PL). Diffraction data confirmed that the crystallite size is around 3-5 nm. Room temperature photoluminescence (PL) spectrum for the bare ZnS sample shows a strong band at ∼445 nm. The uncapped and capped(SHMP, PVP) ZnS:Mn²⁺ samples show a strong and broad band in the ∼580-585 nm range.     

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.     

Nanotwinning in CdS quantum dots

High resolution transmission electron microscopy, X-ray diffraction and photoluminescence measurements are carried out in order to study the defects in CdS quantum dots (QDs), synthesized in cubic phase by chemical co-precipitation method. The nanotwinning structures in CdS quantum dots (∼2.7 nm) are reported for the first time. Mostly CdS QDs are characterized by existence of nanotwin structures. The twinning structures are present together with stacking faults in some QDs while others exist with grain boundaries. Raman spectroscopy analysis shows intense and broad peaks corresponding to fundamental optical phonon mode (LO) and the first over tone mode (2LO) of CdS at 302 cm⁻¹ and 605 cm⁻¹ respectively. A noticeable shift is observed in Raman lines indicating the effect of phonon confinement. Fourier transform infrared spectroscopy analysis confirms the presence of Cd–S stretching bands at 661 cm⁻¹ and 706 cm⁻¹. The photoluminescence spectrum shows emission in yellow and red regions of visible spectrum. The presence of stacking faults and other defects are explained on the basis of X-rays diffraction patterns and are correlated with photoluminescence spectrum. These nanotwinning and microstructural defects are responsible for different emissions from CdS QDs.     

Ar irradiation of Si nanocrystal-doped SiO2: Evolution of photoluminescence

We report the evolution of photoluminescence (PL) of Si nanocrystals (nc-Si) embedded in a matrix of SiO₂ during Ar⁺ ion bombardment. The integrated intensity of nc-Si PL falls down drastically before the Ar⁺ ion fluence of 10¹⁵ ions cm⁻², and then decreases slowly with the increasing ion fluence. At the meantime, the PL peak position blueshifts steadily before the fluence of 10¹⁵ ions cm⁻², and then changes in an oscillatory manner. Also it is found that the nc-Si PL of the Ar⁺-irradiated sample can be partly recovered after annealing at 800 °C in nitrogen, but can be almost totally recovered after annealing in oxygen. The results confirm that the ion irradiation-induced defects are made up of oxygen vacancies, which absorb light strongly. The oscillatory peak shift of nc-Si can be related to a size-distance distribution of nc-Si in SiO₂.     

Luminescence studies on swift heavy ion irradiated nanocrystalline aluminum oxide

Pellets of nanocrystalline aluminum oxide synthesized by a combustion technique are irradiated with 120 MeV Au⁹⁺ ions for fluence in the range 5×10¹¹-1×10¹³ ions cm⁻². Two photoluminescence (PL) emissions, a prominent one with peak at ∼525 nm and a shoulder at ∼465 nm are observed in heat treated and Au⁹⁺ ion irradiated aluminum oxide. The 525 nm emission is attributed to F₂²⁺-centers. The PL intensity at 525 nm is found to increase with increase in ion fluence up to 1×10¹² ions cm⁻² and decreases beyond this fluence. Thermoluminescence (TL) of heat-treated and swift heavy ion (SHI) irradiated aluminum oxide gives a strong and broad TL glow with peak at ∼610 K along with a weak shoulder at 500 K. The TL intensity is found to increase with Au⁹⁺ ion fluence up to 1×10¹³ ions cm⁻² and decreases beyond this fluence.     

Near-infrared emission bands of Er-doped YAP and LSO crystals

The ground state absorption (GSA), photoluminescence (PL) and photoluminescence excitation (PLE) spectra for Er(1.0 at%):YAP and Er(0.5 at%):LSO were measured at room temperature. Based on the GSA spectra, the radiative transition rates and luminescence branch ratios of erbium ions were determined by the Judd-Ofelt (J-O) method. In the range of 1400-1700 nm Er(1.0 at%):YAP has intense absorption at 1509 nm (0.96×10⁻²⁰ cm²), which is almost two times larger than the peak absorption of Er(0.5 at%):LSO. From the PL and PLE spectra, four intense emission bands around 850 nm (⁴S_3/2→⁴I_13/2), 980 nm (⁴I_11/2→⁴I_15/2), 1230 nm (⁴S_3/2→⁴I_11/2) and 1520 nm (⁴I_13/2→⁴I_15/2) were observed. The stimulated emission cross-sections of the four bands were calculated by the Fuchtbauer-Ladenberg (F-L) equation. The results suggest that Er(1.0 at%):YAP has potential to realize laser oscillation at 858 nm because of the relatively large simulated emission cross-section (1.76×10⁻²⁰ cm²). The temperature dependences of the PL spectra for the two crystals were also investigated in the range of 290-12 K. The ∼1520 nm emission presents continuous increase with temperature, while the emissions around 850, 1230 and 980 nm firstly increase with temperature, then reach their own largest values at the transition temperatures (about 100 K), and finally decrease with temperature. These results were well interpreted by the temperature dependence of multi-phonon process.     

Nonlinear optical properties of periodic gold nanoparticle arrays

Periodic Au nanoparticle arrays were fabricated on silica substrates using nanosphere lithography. The identical single-layer masks were prepared by self-assembly of polystyrene nanospheres with radius R = 350 nm. The structural characterization of nanosphere masks and periodic particle arrays was investigated by atomic force microscopy. The nonlinear optical properties of the Au nanoparticle arrays were determined using a single beam z-scan method at a wavelength of 532 nm with laser duration of 55 ps. The results show that periodic Au nanoparticle arrays exhibit a fast third-order nonlinear optical response with the nonlinear refractive index and nonlinear absorption coefficient being n₂ = 6.09 × 10⁻⁶ cm²/kW and β = −1.87 × 10⁻⁶ m/W, respectively.     

Nonlinear optical properties of Au/ZnO nanoparticle arrays

The triangular-shaped Au/ZnO nanoparticle arrays were fabricated on fused quartz substrate using nanosphere lithography. The structural characterization of the Au/ZnO nanoparticle arrays was investigated by atomic force microscopy. The absorption peak due to the surface plasmon resonance of Au particles at the wavelength of about 570 nm was observed. The nonlinear optical properties of the nanoparticle arrays were measured using the z-scan method at a wavelength of 532 nm with pulse duration of 10 ns. The real and imaginary part of third-order nonlinear optical susceptibility, Re χ⁽³⁾ and Im χ⁽³⁾, were determined to be 1.15 × 10⁻⁶ and −5.36 × 10⁻⁷ esu, respectively. The results show that the Au/ZnO nanoparticle arrays have great potential for future optical devices.     

Luminescence property of Ce-doped silica decorated with S and Cl anions

Ce³⁺-doped silica was synthesized by sol-gel technique and was further decorated with S²⁻ and Cl⁻ anions through chemical exchange in controlled ambient at elevated temperature. The structure and optical property of samples were examined by X-ray diffraction spectrum, XPS pattern, reflection pattern, and photoluminescence patterns. There is a broad luminescence band at 445 nm under the excitation at 320 nm in the Ce³⁺-doped silica heat-treated in air at 1000 °C. The heat-treatment of the sample in vacuum at 800 °C can increase the intensity of luminescence but have no effect on the wavelength of luminescence. The decoration of S²⁻ and Cl⁻ anions cannot only increase the luminescent intensity but also shift the luminescent wavelength to shorter wavelength.     

Influence of Au thickness on the optical and electrical properties of transparent and conducting TiO2/Au/TiO2 multilayer films

Au-intermediate TiO₂/Au/TiO₂ (TAT) multilayer films were deposited by RF magnetron sputtering onto glass substrates. Changes in the optical and electrical properties of the films were investigated with respect to the thickness of the Au interlayer.The observed optical and electrical properties were dependent on the thickness of the Au interlayer. The resistivity decreased to 3.3 × 10⁻⁴ Ω cm for TiO₂ films with a 20 nm-thick Au interlayer and the optical transmittance was also influenced by the Au interlayer. Although optical transmittance deteriorated as Au thickness increased, TiO₂ films with a 5 nm-thick Au interlayer showed a relatively high optical transmittance of 80% at a wavelength of 550 nm. In addition, since a TAT film with a 5 nm-thick Au interlayer showed a relatively high work function value, it is an alternative candidate for use as a transparent anode in OLEDs and flat panel displays.     

Blue luminescent silicon nanocrystals prepared by short pulsed laser ablation in liquid media

The pulsed laser processing in liquid media is an attractive alternative to produce room temperature luminescent silicon nanocrystals (Si-ncs). We report on a blue luminescent Si-ncs preparation by using nanosecond pulsed laser (Nd:YAG, KrF excimer) processing in transparent polymer and water. The Si-ncs fabrication is assured by ablation of crystalline silicon target immersed in liquids. During the processing and following aging in liquids, oxide based liquid media, induce shell formation around fresh nanocrystals that provides a natural and stable form of surface passivation. The stable room temperature blue-photoluminescent Si-ncs are prepared with maxima located around ∼440 nm with corresponding optical band gap around ∼2.8 eV (∼430 nm). Due to the reduction of surface defects, the Si-ncs preparation in water, leads to a narrowing of full-width-half-maxima of the photoluminescence spectra.     

Raman spectroscopic and photoluminescence study of single-crystalline SnO2 nanowires

Single-crystalline SnO₂ nanowires with sizes of 4-14 nm in diameter and 100-500 nm in length were produced in a molten salt approach by using hydrothermal synthesized precursor. Structural characters of the nanowires were examined by X-ray diffraction and high-resolution electron transmission microscopy. Raman, photoluminescence and X-ray photoelectron spectra of the samples were examined under heat treatments. Three new Raman modes at 691, 514 and 358 cm⁻¹ were recorded and assigned. The former two are attributed to activation of original Raman-forbidden A_2uLO mode and the third is attributed to defects in small-sized nanowires. A strong photoluminescence is observed at about 600 nm, the temperature effects is examined and the origin of the PL process is discussed via X-ray photoelectron spectra.     

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.     

1.54 μm room temperature emission from Er-doped Si nanocrystals deposited by ECR-PECVD

In this work, silicon nanocrystals (Si-nc) embedded in a silicon-rich silicon oxide (SRSO) matrix doped with Er³⁺ ions for different erbium and silicon concentrations have been deposited by electron-cyclotron resonance plasma-enhanced chemical-vapor-deposition (ECR-PECVD) technique. Their optical properties have been investigated by photoluminescence (PL) and reflectance spectroscopy.Room temperature emission bands centered at ∼1.54 and at 0.75 μm have been obtained for all samples. The most intense emission band at ∼1.54 μm was obtained for samples with concentrations of 0.45% and 39% for erbium and silicon, respectively. Moreover, it has been found that the broad emission band centered at ∼0.75 μm for all samples shows a very strong interference pattern related to the a specific sample structure and a high sample quality.     

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.