Tunable deep-level emission in ZnO nanoparticles via yttrium doping

Yttrium-doped ZnO nanoparticles (Zn_1−xY_xO, x = 0, 0.03, 0.05) were synthesized by sol-gel technique. The effects of yttrium doping concentration on the structures, morphologies and optical properties of as-synthesized Zn_1−xY_xO nanoparticles were investigated in detail. The results from structural characterizations clearly demonstrated that yttrium ions were successfully doped into the crystal lattice of ZnO matrix. Besides a UV emission centered at ∼383 nm, the PL spectra of all the samples exhibited a broad deep-level emission, which can be deconvoluted into two Gauss peaks centered at 539 nm (P1) and 598 nm (P2), respectively. As the concentration of Y doping increased from 0% to 5%, the peak position with maximum intensity in deep-level emission band was gradually tuned from 539 nm to 598 nm and the relative intensity ratio of I_P1/I_P2 also decreased step by step, which revealed a unique optical property of yttrium-doped ZnO nanoparticles.     

Formation of ZnO nanorod arrays on polytetraflouroethylene (PTFE) via a seeded growth low temperature hydrothermal reaction

ZnO nanorod arrays were formed by a low temperature hydrothermal process on seeded polytetraflouroethylene (PTFE) sheets. The seed layer was formed using thermal oxidation of a thin evaporated Zn film on the PTFE sheet at 300 °C in air for 10 min. The formation of ZnO nanorod arrays in the hydrothermal reactive bath consisting of hexamethylamine (HMT) and Zn ions occurred via the reaction of hydroxyl ions released during the thermal degradation of HMT with the Zn ions. The seed layer provided a template for the nucleation of the ZnO and HMT which also acted as a chelating agent that promoted growth of the ZnO along the c-axis, leading to the formation of exclusively (0 0 2) ZnO nanorods. The effect of exposure time of the seeded PTFE to the reactive solution on the formation of the nanorods was investigated. Well aligned, relatively uniform tapered 300 nm long nanorods can be formed after 8 h of exposure. Longer exposure times to 24 h resulted in the formation of more uniform nanorods with base diameter averaged of ∼100 nm and the tip diameter of ∼50 nm. XRD analysis showed that the ZnO nanorod array had a hexagonal wurtzite structure. This result is in agreement with HR-TEM observations and Raman scattering analysis. Photoluminescence study showed that a strong UV emission peak was obtained at 380 nm and a small peak at 560 nm, which is associated with green emission. The optical band gap measured from these plots was at 3.2 eV on average.     

New process for synthesis of ZnO thin films: Microstructural, optical and electrical characterization

Nanocrystalline ZnO thin films were prepared on glass substrates by using spin coating technique. The effect of annealing temperature (400-700 °C) on structural, compositional, microstructural, morphological, electrical and optical properties of ZnO thin films were studied by X-ray diffraction (XRD), Energy dispersive Spectroscopy (EDS), Atomic Force Microscopy (AFM), High Resolution Transmission Microscopy (HRTEM), Scanning Electron Microscopy (SEM), Electrical conductivity and UV-visible Spectroscopy (UV-vis). XRD measurements show that all the films are nanocrystallized in the hexagonal wurtzite structure and present a random orientation. The crystallite size increases with increasing annealing temperature. These modifications influence the optical properties. The AFM analysis revealed that the surface morphology is smooth. The HRTEM analysis of ZnO thin film annealed at 700 °C confirms nanocrystalline nature of film. The SEM results shows that a uniform surface morphology and the nanoparticles are fine with an average grain size of about 40-60 nm. The dc room temperature electrical conductivity of ZnO thin films were increased from 10⁻⁶ to 10⁻⁵ (Ω cm)⁻¹ with increase in annealing temperature. The electron carrier concentration (n) and mobility (μ) of ZnO films annealed at 400-700 °C were estimated to be of the order of 4.75-7.10 × 10¹⁹ cm⁻³ and 2.98-5.20 × 10⁻⁵ cm² V⁻¹ S⁻¹.The optical band gap has been determined from the absorption coefficient. We found that the optical band gap energy decreases from 3.32 eV to 3.18 eV with increasing annealing temperature between 400 and 700 °C. This means that the optical quality of ZnO films is improved by annealing.It is observed that the ZnO thin film annealing at 700 °C has a smooth and flat texture suited for different optoelectronic applications.     

A facile route to well-dispersed single-crystal silver nanoparticles from [AgSO3] in water

Well-dispersed single-crystal Ag nanoparticles (NPs) were synthesized through a simple hydrothermal strategy in an aqueous solution of [AgSO₃]⁻. The obtained Ag NPs are quasispherical in shape and the diameter of particles is ranging from 35 to 50 nm with a narrow size distribution. The proper choices of [AgSO₃]⁻ as precursor and PVP as stabilizer are the keys to the formation of Ag NPs. A possible formation mechanism was proposed. And the optical absorption property of the obtained Ag NPs was also investigated. The as-prepared Ag NPs exhibit an absorption band at ca. 430 nm, which is the characteristic surface plasmon resonance of spherical/quasispherical Ag NPs.     

Absorption-emission study of hydrothermally grown Al:ZnO nanostructures

The preparation, structural characterization and optical properties of aluminum doped ZnO (Al:ZnO) nanostructures grown under hydrothermal method are reported. One-dimensional (1-D) growth is achieved by the controlled addition of metal nitrate as precursors in the presence of long chain surfactant, poly-ethylene glycol (PEG) at 160 °C for 20 h. The as-synthesized ZnO rods are single crystalline, exhibiting an oriented growth along [001] direction. The Al6 rod has an aspect ratio of 3.2, which can be effectively applied in optoelectronic devices. Comprehensive structural analysis using X-ray diffraction method (XRD) and Energy dispersive X-ray analysis (EDX) indicate that the dopant Al atom occupies Zn sites in ZnO and the elemental composition of Al is consistent with the amount utilized in the hydrothermal synthesis. XRD shows that the Al:ZnO nanostructures from 1 to 9 atomic percent (at.%) has hexagonal wurtzite structure of ZnO. The Al dopant effects on lattice vibration and electronic transitions of the ZnO nanostructures have been investigated by Fourier transform Infrared spectroscopy (FT-IR), Ultraviolet-visible (UV-vis) absorption spectroscopy and photoluminescence (PL) emission recorded at room temperature. The correlation existing between absorption and emission study tell that their characteristic band edge peak of doped ZnO shifts towards higher wavelength side for 3-9 at.% with respect to Al0 thus, exhibiting a red shift phenomenon with decrease in optical bandgap. The observed PL reveals two emission peaks centered at 374 nm and 530 nm. The near band edge (NBE) to defect emission ratio increases with dopant concentration indicating the linear enhancement in crystal quality and declination in zinc vacancies from 3 to 9 at.% of Al.     

Synthesis and luminescence studies of CdSrS nanostructures

Cadmium strontium sulfide nanostructures were synthesized by solid state diffusion method in the presence of sodium thiosulfate. XRD confirmed the presence of CdS and SrS structures in the synthesized samples. TEM micrographs revealed the formation of nearly spherical nanoparticles with grain size in the range 30-40 nm. The PL emission was centred around 532 nm with a shoulder at 468 nm. The PL emission of CdSrS shows a blue shift in comparison to that of CdS. Substantially enhanced photoluminescence emission was observed with the addition of Bi³⁺ as a dopant. The effects of different excitation wavelengths on the PL spectra have also been investigated. It is suggested that the emission processes are linked to divalent Cd ions with broadening resulting due to these ions in being differing ion environments.     

Field emission enhancement of ZnO nanorod arrays with hafnium nitride coating

Vertically well-aligned single crystal ZnO nanorod arrays were synthesized and enhanced field electron emission was achieved with hafnium nitride (HfN_x) coating under proper sputtering condition. HfN_x films with various composition have been coated on ZnO nanorod arrays using a reactive direct current (DC) magnetron sputtering system. Morphology and crystal configuration of the ZnO nanorod arrays were investigated by scanning electron microscopy and X-ray diffraction. The field emission properties of the coated and uncoated ZnO nanorod arrays were characterized. The as-grown ZnO nanorod arrays showed a turn-on electric field of 6.60 V μm^− 1 at a current density of 10 μA cm^− 2 and an emission current density of 1 mA cm^− 2 under the field of 9.32 V μm^− 1. While the turn-on electric field of the coated ZnO nanorod arrays sharply decreased to 2.42 V μm^− 1, an emission current density of 1 mA cm^− 2 under the field of only 4.30 V μm^− 1 can be obtained. A method to accurately measure the work function of the coated films was demonstrated.     

One-step synthesis and properties of monolithic photoluminescent ruby colored cuprous oxide antimony oxide glass nanocomposites

Cuprous oxide (Cu₂O) antimony glass (K₂O-B₂O₃-Sb₂O₃) monolithic nanocomposites having brilliant yellow to ruby red color have been synthesized by a single-step melt-quench technique involving in situ thermochemical reduction of Cu²⁺ (CuO) by the reducing glass matrix without using any external reducing agent. The X-ray diffraction (XRD), infrared transmission and reflection spectra, and selected area electron diffraction analysis support the reduction of Cu²⁺ to Cu⁺ with the formation of Cu₂O nanoclusters along with Cu_ySb_2−x(O,OH)_6-7 (y ≤ 2, x ≤ 1) nanocrystalline phases while Cu⁰ nanoclusters are formed at very high Cu concentration. The UV-vis spectra of the yellow and orange colored nanocomposites show size-controlled band gap shift of the semiconductor (Cu₂O) nanocrystallites embedded in the glasses while the red nanocomposite exhibits surface plasmon resonance band at 529 nm due to metallic Cu. Transmission electron microscopic image advocates the formation of nanocystallites (5-42 nm). Photoluminescence emission studies show broad red emission band around 626 nm under various excitation wavelengths from 210 to 270 nm.     

Optical properties of antimony-implanted ZnO epilayers

Antimony ions were implanted into ZnO films grown on c-plane sapphire by pulsed-laser deposition. Raman scattering modes of the Sb-implanted samples were found to be influenced by the implantation dose. A characteristic peak at 576 cm^− 1 was observed with an asymmetric shape due to ion damage to the lattice of the implanted ZnO films. When the implant dose was low, the height of the peak was reduced by rapid thermal annealing at 400-600 °C and the symmetry of the spectra was recovered. However, when the Sb dose exceeded 1 × 10¹⁵ cm^− 2, the peak maintained unchanged after rapid thermal annealing at temperatures up to 600 °C. A broad and low Raman peak was observed at 437 cm^− 1, which is related to the surface damage caused by the energetic ion bombarding. Photoluminescence measurement showed a decrease of the bandedge emission at 3.36 eV, a clear effect of defects induced by the implantation, and confirmed partial recovery of the crystal by rapid annealing.     

Preparation and luminescent properties of Eu doped Sr3La(PO4)3 phosphor

Eu²⁺-doped Sr₃La(PO₄)₃ phosphors were synthesized by solid-state reaction method. Their luminescent properties were investigated. The phosphor could be excited by ultraviolet light effectively. The emission spectra exhibit two emission peaks located at 418 nm and 500 nm, respectively. These two peaks originated from two different luminescent centers, respectively. One is nine-coordinated Eu(I) center, other is six-coordinated Eu(II) center. It was found that the doping concentration of Eu²⁺ ions affected the shape of emission spectra. As the doping concentration increasing, Eu²⁺ ions are more likely to form Eu(I) luminescent centers and emit purple light.     

Fabrication and luminescence properties of In2O3-capped ZnS nanowires

ZnS-core/In₂O₃-shell nanowires have been prepared by using a two-step process: thermal evaporation of ZnS powders on Si(1 0 0) substrates coated with Au thin films and sputter-deposition of In₂O₃. The ZnS nanowires were a few tens of nanometers in diameter and a few hundreds of micrometers in length. ZnS nanowires have an emission band centered at approximately 570 nm in the yellow region. The yellow emission has been enhanced in intensity by capping the ZnS nanowires with In₂O₃ presumably due to the increase in the concentrations of indium and oxygen interstitials in the very surface region of the ZnS cores and further enhanced by annealing in a reduction atmosphere maybe because of the increase in the concentration of Au_Zn⁻ in the ZnS cores. In contrast, the yellow emission intensity has been decreased by annealing in an oxidation atmosphere due to the conversion of ZnS into ZnO as a result of the reaction of ZnS in the cores with oxygen.     

Synthesis and characterization of Er doped CaF2 nanoparticles

Er³⁺ doped CaF₂ nanoparticles were synthesized by a chemical co-precipitation method. Effect of the dopant concentrations on the structure and optical properties of the CaF₂ nanoparticles was investigated. The X-ray powder diffraction and transmission electron microscopy analysis was used to characterize the structure and morphology of the nanoparticles. The nanoparticles with different dopant concentration exhibited a sphere-like morphology with diameters of about 8-36 nm. The incorporation of Er³⁺ ions into CaF₂ resulted in the decrease in grain size and deterioration of crystallinity, but enlarged the lattice constants of CaF₂. Additional annealing treatment at 400 °C to the prepared CaF₂ removed the NO₃⁻ and OH⁻ groups adsorbed on the particles’ surfaces, and improved the optical properties of the nanoparticles. The fluorescence intensity, with a maximum at approximately 0.4 mol%, decreased with the increase in doping concentration because of concentration quenching.     

Synthesis and photoluminescence of a novel Sr-SiAlON:Eu blue-green phosphor (Sr14Si68−sAl6+sOsN106−s:Eu (s ≈ 7))

A novel Eu²⁺ activated Sr-SiAlON oxynitride phosphor, with the chemical composition of Sr₁₄Si_68−sAl_6+sO_sN_106−s:Eu²⁺ (s ≈ 7), was synthesized by firing the powder mixture of SrO, SrSi₂, α-Si₃N₄, AlN and Eu₂O₃ at 1900 °C for 6 h under 1 MPa nitrogen atmosphere. The structure has a typical feature of SiAlON consisting of the host framework which is constructed by a three-dimensional MX₄ tetrahedral (M: Si or Al; X: O or N) network, and Sr or Eu²⁺ ions as the guest ions. It has been shown that the Sr-SiAlON:Eu²⁺ phosphor has the excitation band covering the range of the ultraviolet light region to 500 nm, and exhibits an intense blue-green color with the emission band centered at about 508 nm. The temperature dependent emission intensity of the Sr-SiAlON:Eu²⁺ phosphor is better than that of a typical blue-green Ba₂SiO₄:Eu²⁺ phosphor. It is demonstrated that Sr-SiAlON:Eu²⁺ phosphor is very promising for use in white -LEDs.     

Synthesis of cadmium oxide doped ZnO nanostructures using electrochemical deposition

Ternary ZnCdO alloy semiconductor nanostructures were grown using electrochemical deposition. Crystalline nanostructures/nanorods with cadmium concentration ranging from 4 to 16 at% in the initial solution were electrodeposited on tin doped indium oxide (ITO) conducting glass substrates at a constant cathodic potential −0.9 V and subsequently annealed in air at 300 °C. X-ray diffraction measurements showed that the nanostructures were of wurtzite structure and possessed a compressive stress along the c-axis direction. The elemental composition of nanostructures was confirmed by energy dispersive spectroscopy (EDS). ZnO nanostructures were found to be highly transparent and had an average transmittance of 85% in the visible range of the spectrum. After the incorporation of Cd content into ZnO the average transmittance decreased and the bandgap tuning was also achieved.     

Radiotracer study of embedding of SO4 and Cl ions into the surface film formed on Mn corroding in perchlorate solution

The adsorption of radiolabelled Cl⁻ and SO₄⁻ ions from aqueous perchlorate solutions onto powdered Mn metal was studied. It was found that the extent of the adsorption is determined by the continuous increase of the thickness of the surface oxide/hydroxide layer formed as a consequence of the slow corrosion of the metal in neutral or quasi-neutral media. At low pH values (pH < 6) the extent of the adsorption decrease significantly owing to the dissolution of the surface layer. At high pH values (pH > 10) the adsorption decreases presumably owing to the competitive adsorption of OH⁻ ions or the modification of the adsorption centres by some kind of deprotonation.     

Luminescence properties of Ca10K(PO4)7:RE (RE = Ce, Tb, Dy, Tm and Sm) under vacuum ultraviolet excitation

A series of RE³⁺ (RE = Ce, Tb, Dy, Tm and Sm) activated Ca₁₀K(PO₄)₇ were synthesized by conventional state reaction and their photoluminescence properties under vacuum ultraviolet excitation were investigated. The PO₄³⁻ absorption lies within the range from 125 to 180 nm in all the excitation spectra of Ca₁₀K(PO₄)₇:RE³⁺. The first f-d transition of Ce³⁺ is observed at 316 nm, and the Ce³⁺ emission is located at about 350 nm. Both the first spin-allowed and spin-forbidden f-d transitions of Tb³⁺ are situated at 232 and 263 nm, respectively. The emission spectrum of Ca₁₀K(PO₄)₇:Tb³⁺ exhibits typical Tb³⁺ emissions with the predominant peak at 544 nm. The O²⁻-Dy³⁺ charge transition band was calculated and identified around 173 nm, the CIE chromaticity coordinates of Dy³⁺ were calculated to be 0.364 and 0.392. The Ca₁₀K(PO₄)₇:Tm³⁺ demonstrates the strongest excitation at about 182 nm assigned to O²⁻-Tm³⁺, and gives the predominant emission at 453 nm. The ⁴G_5/2-⁶H_7/2 transition of Sm³⁺ at 601 nm is the most intensive in the emission spectrum.     

Preparation, structure and photoluminescence of nanoscaled-Nd: Lu3Al5O12

Nd:Lu₃Al₅O₁₂ (Nd:LuAG) nano-crystalline was synthesized by co-precipitation method. Its phase transformation, structure, absorption and photoluminescence properties were studied. The Nd:LuAG polycrystalline phase is formed above 900 °C and its particle sizes are in the range of 18-36 nm. The structure of Nd:LuAG was refined by Rietveld method. The lattice parameters and the distortion of Lu³⁺-O²⁻ polyhedron in Nd:LuAG are larger than that of in pure LuAG. Because the distortion of Lu³⁺-O²⁻ polyhedron is larger than that of Y³⁺-O²⁻ polyhedron in YAG and the distance of Lu³⁺-O²⁻ is smaller than that of Y³⁺-O²⁻ in YAG, Nd³⁺ in LuAG experiences a stronger crystal field effect, which is proved by the crystal field strength and the chemical environment parameter. The absorption spectrum shows that Nd:LuAG has a broad absorption band at 808 nm with FWHM above 6 nm, which is favorable for improving laser efficiency. The fluorescence lifetime from ⁴F_3/2 → ⁴I_11/2 transition is 320 μs and longer than that of Nd:YAG. The longer lifetime is propitious to energy storage. The emission cross section at 1064 nm is 2.89 × 10⁻¹⁹ cm², taking into account the Boltzmann distribution of the excited state. The emission cross section in Nd:LuAG is also larger than that of Nd:YAG, which is useful for laser operation. All results indicate that Nd:LuAG is a promising crystal material to apply in high energy lasers.     

Filtered vacuum arc deposition of undoped and doped ZnO thin films: Electrical, optical, and structural properties

Filtered vacuum (cathodic) arc deposition (FVAD, FCVD) of metallic and ceramic thin films at low substrate temperature (50-400 °C) is realized by magnetically directing vacuum arc produced, highly ionized, and energetic plasma beam onto substrates, obtaining high quality coatings at high deposition rates. The plasma beam is magnetically filtered to remove macroparticles that are also produced by the arc. The deposited films are usually characterized by their good optical quality and high adhesion to the substrate. Transparent and electrically conducting (TCO) thin films of ZnO, SnO₂, In₂O₃:Sn (ITO), ZnO:Al (AZO), ZnO:Ga, ZnO:Sb, ZnO:Mg and several types of zinc-stannate oxides (ZnSnO₃, Zn₂SnO₄), which could be used in solar cells, optoelectronic devices, and as gas sensors, have been successfully deposited by FVAD using pure or alloyed zinc cathodes. The oxides are obtained by operating the system with oxygen background at low pressure. Post-deposition treatment has also been applied to improve the properties of TCO films.The deposition rate of FVAD ZnO and ZnO:M thin films, where M is a doping or alloying metal, is in the range of 0.2-15 nm/s. The films are generally nonstoichiometric, polycrystalline n-type semiconductors. In most cases, ZnO films have a wurtzite structure. FVAD of p-type ZnO has also been achieved by Sb doping. The electrical conductivity of as-deposited n-type thin ZnO film is in the range 0.2-6 × 10^− 5 Ω m, carrier electron density is 10²³-2 × 10²⁶ m^− 3, and electron mobility is in the range 10-40 cm²/V s, depending on the deposition parameters: arc current, oxygen pressure, substrate bias, and substrate temperature. As the energy band gap of FVAD ZnO films is ∼ 3.3 eV and its extinction coefficient (k) in the visible and near-IR range is smaller than 0.02, the optical transmission of 500 nm thick ZnO film is ∼ 0.90.     

Electrochemical behaviour of microcrystalline aluminium in neutral fluoride containing solutions

The electrochemical behaviour of microcrystalline pure aluminium coating (mc-Al), fabricated by a magnetron sputtering technique, has been investigated in NaF as well as NaF + NaCl aqueous solutions. Results indicate that the anodic polarization characteristic changes with NaF concentration. F⁻ anions promote the formation of a passive film, whose semiconducting properties were investigated. When the F⁻ concentration is high ([F⁻] ? 0.03 mol/L) the passive film is mainly composed of aluminium fluoride, which is an n-type semiconductor on mc-Al and a p-type semiconductor on polycrystalline Al (pc-Al). In NaF + NaCl aqueous solutions, Cl⁻ and F⁻ ions compete in affecting the type of semiconducting passive films formed on mc-Al.     

Vacuum ultraviolet spectroscopic properties of KSrPO4:Tb

KSrPO₄:Tb³⁺ phosphors were prepared by a solid-state method and their photoluminescence properties were investigated under vacuum ultraviolet excitation. In the excitation spectrum monitoring at 544 nm, the band in the region of 120-162 nm can be attributed to be the overlap of host absorption and charge transfer transition of O²⁻ → Tb³⁺, and the band ranging from 162 to 300 nm was assigned to the f-d transition of Tb³⁺. The photoluminescence spectrum shows that the phosphors exhibited a strong green emission around 544 nm corresponding to the ⁵D₄ → ⁷F₅ transition of Tb³⁺ under the excitation of 147 nm. Optimal emission intensity was obtained when x = 7% in KSr_1-xPO₄:xTb³⁺ and the luminescent chromaticity coordinates were calculated to be (x = 0.317, y = 0.522) for KSr_0.93PO₄:7%Tb³⁺.