Characterization and luminescent properties of SiO2:ZnS:Mn and ZnS:Mn nanophosphors synthesized by a sol-gel method

ZnS and SiO₂-ZnS nanophosphors, with or without different concentration of Mn²⁺ activator ions, were synthesized by using a sol-gel method. Dried gels were annealed at 600 °C for 2 h. Structure, morphology and particle sizes of the samples were determined by using X-ray diffraction (XRD), highresolution transmission electron microscopy (HRTEM) and field emission scanning electron microscopy (FESEM). The diffraction peaks associated with the zincblende and the wurtzite structures of ZnS were detected from as prepared ZnS powders and additional diffraction peaks associated with ZnO were detected from the annealed powders. The particle sizes of the ZnS powders were shown to increase from 3 to 50 nm when the powders were annealed at 600 °C. An UV-Vis spectrophotometer and a 325 nm He-Cd laser were used to investigate luminescent properties of the samples in air at room temperature. The bandgap of ZnS nanoparticles estimated from the UV-Vis data was 4.1 eV. Enhanced orange photoluminescence (PL) associated with ⁴T₁→⁶A₁ transitions of Mn²⁺ was observed from as prepared ZnS:Mn²⁺and SiO₂-ZnS:Mn²⁺ powders at 600 nm when the concentration of Mn²⁺ was varied from 2-20 mol%. This emission was suppressed when the powders were annealed at 600 °C resulting in two emission peaks at 450 and 560 nm, which can be ascribed to defects emission in SiO₂ and ZnO respectively. The mechanism of light emission from Mn²⁺, the effect of varying the concentration on the PL intensity, and the effect of annealing are discussed.     

Microphotoluminescence study of local temperature fluctuations in n-type (Cd,Mn)Te quantum well

Microphotoluminescence mapping measurements were performed in a magnetic field on a (Cd,Mn)Te quantum well, modulation n-doped with iodine at about 10¹⁰ cm⁻². Photoluminescence spectra contain neutral (X⁰) and negatively charged (X⁻) exciton lines. The Zeeman effect shows a significant role of heating of the Mn system even under lowest excitation densities. The effective temperature of the magnetic system exhibits strong fluctuations anticorrelated with the total intensity of PL signal. An interpretation of these fluctuations in terms of the influence of non-radiative recombination centers is proposed (in two alternative versions). Maps of the local X⁰/X⁻ intensity ratio indicate a minor role of electrostatic potential fluctuations.     

Localization of nonequilibrium current carriers close to Cr ions in ZnSe:Cr single crystals

The photoluminescence (PL) of Cr-doped ZnSe single crystals is investigated in a temperature interval from 83 up to 297 K and in a wavelengths region from 440 up to 2700 nm. The doping was carried out during a high-temperature annealing of ZnSe crystals in CrSe vapors and in chrome chlorides medium. It is revealed that the doping results in an appearance of both luminescence bands located at 0.54, 0.97, and 2.15 μm and edge luminescence bands located at 454, 457, and 460 nm at 83 K. It is shown that the PL bands located at 457 and 460 nm are caused by the radiative recombination with the participation of holes located on hydrogen-like orbits close to Cr⁺ centers, having a binding energy of 99 meV. The excitons bound with centers responsible for the radiation located at 0.54 μm and having a binding energy of 65-68 meV are considered. The energy of a lattice relaxation at recharge of centers responsible for green radiation is estimated and equals 40-170 meV.     

Three-photon upconversion luminescence phenomenon for the green levels in Er/Yb codoped cubic nanocrystalline yttria

In this paper, we observed that in Er³⁺/Yb³⁺ codoped nanocrystals (NC), with the decreasing particle size and the increasing Yb³⁺ concentration, the upconversion luminescence (UCL) of the red emissions of gradually increased, while the green emissions of gradually diminished under 980 nm diode laser excitation. In NC with lower Yb³⁺ concentration, both the red and green emissions result from a two-photon excitation. In NC with higher Yb³⁺ concentration, the red emissions result from a two-photon excitation, while the green emissions dominantly result from a three-photon excitation. A model was provided for explaining the above UCL phenomena.     

Micro-photoluminescence study of electron-spin injection in self-assembled semiconductor quantum dots

We present a micro-photoluminescence (m-PL) study of electron-spin injection under magnetic fields in self-assembled semiconductor quantum dots (QDs) of CdSe. A characteristic band line-up of the CdSe QDs coupled with a diluted magnetic semiconductor quantum well (DMS-QW) of ZnCdMnSe through a ZnSe barrier layer enabled us to inject the electron spins from the DMS-QW into QDs. An experimental evidence of the electron-spin injection was provided by observations of circularly polarized m-PL spectra from individual QDs in this coupled QD structure. We find anti-correlation of PL intensity in between the DMS-QW (spin injector) and the individual QDs (spin receiver).     

Photoluminescence of the ZnSe single crystals doped by thermal diffusion of nitrogen

Photoluminescence (PL) spectra of ZnSe single crystals annealed in different ambients containing molecular nitrogen are investigated. The compensating activity of N impurity in n-ZnSe crystals is shown. It is caused by the formation of N_Se acceptor centers, having 101-108 meV activation energy. The intensity of amplification of both long-wave luminescence spectra bands and the edge luminescence spectra bands caused by the presence of nitrogen in annealing medium is investigated. The presented results allow one to assign the long-wave luminescence to deep acceptors caused by uncontrollable impurities, and the relevant bands of the edge luminescence spectra to the excitons bound with the same deep acceptors. The model explaining the transformations of the luminescent properties of ZnSe crystals by means of nitrogen impurity doping is proposed. The model considers the presence of donors having 75 meV activation energy, acceptors having 220-720 meV activation energy and centers having levels localized near the middle of the band gap.     

Donor-acceptor pair luminescence in nitrogen-doped ZnO films grown on lattice-matched ScAlMgO4 (0001) substrates

We have grown nitrogen-doped ZnO (ZnO:N) films by laser molecular-beam epitaxy. The use of lattice-matched ScAlMgO₄ substrates prevented the degradation of crystallinity induced by the nitrogen incorporation to the films. Despite this improvement, we have not obtained ZnO:N films which showed p-type conductivity. We studied the optical properties of these ZnO:N films. Donor-acceptor pair (DAP) luminescence was observed. The results indicate the formation of an acceptor state. The energy position of the DAP luminescence is lower than that reported by Look et al. [Appl. Phys. Lett. 81 (2002) 1830]. The DAP luminescence band shifts to lower energy with increasing nitrogen concentration. A photoluminescence recombination possibly due to the free-electron-to-acceptor (FA) transition was observed at temperatures higher than 40 K. The acceptor ionization energy was estimated from the energy position of the FA luminescence to be 266 meV.     

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.     

Energy levels of vanadium ions in CdTe

In CdTe doped with vanadium the photoluminescence due to the ³ T ₂(F) ³ A ₂(F) transition of V³⁺(d ²) is detected. Its decay time is determined as (630±20) s, a result comparable to the analogous emissions in various host lattices. Further emissions around 5000 cm^–1 and 9000 cm^–1 are caused by charge-transfer transitions or bound-exciton decay. Excitation and sensitization spectra yield information on the positions of the energy levels within the gap, which are discussed using two different models. At T=4.2 K, the distance of the V²⁺/V³⁺ donor level is 7300 cm^–1 and 5700 cm^–1 referred to the valence and the conduction band edges, respectively. The absence of V²⁺(d ³) centres is tentatively ascribed to the existence of deeply bound excitons.     

Auger and photoluminescence analysis of ZnO nanowires grown on AlN thin film

ZnO nanowires were grown on AlN thin film deposited on the glass substrates using a physical vapor deposition method in a conventional tube furnace without introducing any catalysts. The temperature of the substrates was maintained between 500 and 600 °C during the growth process. The typical average diameters of the obtained nanowires on substrate at 600 and 500 °C were about 57 and 22 nm respectively with several micrometers in length. X-ray diffraction and Auger spectroscopy results showed Al diffused from AlN thin film into the ZnO nanowires for the sample grown at 600 °C. Photoluminescence of the nanowires exhibits appearance of two emission bands, one related to ultraviolet emission with a strong peak at 380-382 nm, and the other related to deep level emission with a weak peak at 503-505 nm. The ultraviolet peak of the nanowires grown at 500 °C was blue shifted by 2 nm compared to those grown at 600 °C. This shift could be attributed to surface effect.     

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.     

The fluorescence rate of a single molecule close to a spherical metallic nanoparticle

The theoretical study of fluorescence rate of a single molecule close to a spherical metallic nanoparticle is presented. The dielectric function of the metallic nanoparticle and its polarizability is analyzed when the radii of the nanoparticle is rather small. Based on dipole–dipole model, the distance dependence of the excitation rate, radiation rate, nonradiation rate and quantum yield of the emitter molecule are derived out. The results show that the quantum yield is rather small at the vicinity of the metallic nanoparticle surface.     

Structural, Optical and Electrical Properties of ZnS/Porous Silicon Heterostructures

ZnS films are deposited by pulsed laser deposition on porous silicon （PS） substrates formed by electrochemical anodization of p-type （100） silicon wafer. Scanning electron microscope images reveal that the surface of ZnS films is unsmoothed, and there are some cracks in the ZnS films due to the roughness of the PS surface. The x-ray diffraction patterns show that the ZnS films on PS surface are grown in preferring orientation along cubic phase β-ZnS （111） direction. White light emission is obtained by combining the blue-green emission from ZnS films with the orange-red emission from PS layers. Based on the I-V characteristic, the ZnS/PS heterojunction exhibits the rectifying junction behaviour, and an ideality factor n is calculated to be 77 from the I-V plot.     

Photoluminescence properties of Co-doped ZnO nanocrystals

We performed photoluminescence experiments on colloidal, Co²⁺-doped ZnO nanocrystals in order to study the electronic properties of Co²⁺ in a ZnO host. Room temperature measurements showed, next to the ZnO exciton and trap emission, an additional emission related to the Co²⁺ dopant. The spectral position and width of this emission does not depend on particle size or Co²⁺ concentration. At 8 K, a series of ZnO bulk phonon replicas appear on the Co²⁺-emission band. We conclude that Co²⁺ ions are strongly localized in the ZnO host, making the formation of a Co²⁺d-band unlikely. Magnetic measurements revealed a paramagnetic behaviour.     

Effects of annealing atmosphere on the luminescent efficiency of ZnTe:O phosphors

The effect of the annealing atmosphere on the luminescent efficiency of ZnTe:O phosphors for X-ray imaging applications was studied. The phosphors were doped by ball-milling bulk ZnTe crystals in an O₂ atmosphere and annealed in various atmospheres: vacuum, N₂ or forming gas (95%N₂/5%H₂). All samples exhibited a deep red emission centered at 680 nm.The samples annealed in forming gas atmosphere exhibited an X-ray luminescent efficiency five times higher than the samples annealed in vacuum or N₂ atmospheres, which was attributed to the removal of surface tellurium oxides.     

Syntheses of nanocrystalline BaTiO3 and their optical properties

Stoichiometric and titanium-excess nanocrystalline barium titanates were synthesized using a hydrothermal process at various hydrothermal temperatures and with further heat treatment at 500 °C and 900 °C. Owing to the different process conditions, the excess titanium exists in different states and configurations within the nanocrystalline BaTiO₃ matrix; this was demonstrated by X-ray diffraction, Raman scattering, and photoluminescence. In these nanocrystalline BaTiO₃, the 590, 571, 543 and 694 nm light emission bands were observed; mechanisms leading to such emissions were also discussed. Received: 23 February 2001 / Accepted: 10 May 2001 / Published online: 27 June 2001     

Chemical role of amines in the colloidal synthesis of CdSe quantum dots and their luminescence properties

The role of organic amines in the colloidal synthesis of CdSe quantum dots (QDs) has been studied. CdSe QDs were synthesized from the source solutions containing 5 vol% of amines having various alkyl chain lengths, stereochemical sizes and electron donation abilities. The role of the additional amines was evaluated on the basis of the photoluminescence (PL) properties such as PL wavelength and intensity of the obtained CdSe QDs. The observed PL spectra were explained by the fact that the amines behaved as capping ligands on the surface of the QDs in the product colloidal solution and complex ligands for cadmium in the source solutions. It was shown that the particle size was controlled by the diffusion process depending on the mass and stereochemical shape of the amines, and the luminescence intensity increased with the increasing electron donation ability and capping density of the amines.     

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.     

Photoluminescence and absorption in sol-gel-derived ZnO films

Highly c-axis-oriented ZnO films were obtained on corning glass substrate by sol-gel technique. The characteristics of photoluminescence (PL) of ZnO, as well as the exciton absorption in the absorption (UV) spectra are closely related to the post-annealing treatment. The difference between PL peak position and the absorption edge, designated as Stokes shift, is found to decrease with the increase of annealing temperature. The minimum Stokes shift is about 150 meV. The decrease of Stokes shift is attributed to the decrease in carrier concentration in ZnO film with annealing. X-ray diffraction, surface morphology and refractive index results indicate an improvement in crystalline quality with annealing. Annealed films also exhibit a green emission centered at ∼520 nm with activation energy of 0.89 eV. The green emission is attributed to the electron transition from the bottom of the conduction band to the antisite oxygen O_Zn defect levels.     

Synthesis and luminescence behavior of Eu-doped CaF2 nanoparticles

Luminescent Ca_1−xF_2+x:Eu_x nanoparticles were synthesized by a chemical co-precipitation method in an ethanol solution. The Ca_1−xF_2+x:Eu_x nanoparticles exhibit a sphere-like morphology with particle diameter of about 15-20 nm. With increasing concentration of Eu³⁺ ion the intensity of XRD diffraction peaks decreased significantly and full width at half-maximum of the peaks increased gradually, which indicated that more Eu³⁺ ions resulted in the increase of structural defects. The emission spectrum of Ca_1−xF_2+x:Eu_x nanoparticles consisted of a few narrow, sharp lines corresponding to Eu³⁺ ions. The luminescence intensity of Ca_1−xF_2+x:Eu_x nanoparticles increased with increasing concentration of Eu³⁺ ion and reached a maximum at approximately 15 mol%.