Characterization of ZnO-SnO2 thin film composites prepared by pulsed laser deposition

Thin films of ZnO-SnO₂ composites have been deposited on Si(1 0 0) and glass substrates at 500 °C by pulsed laser ablation using different composite targets with ZnO amount varying between 1 and 50 wt%. The effect of increasing ZnO-content on electrical, optical and structural properties of the ZnO-SnO₂ films has been investigated. X-ray diffraction analysis indicates that the as-deposited ZnO-SnO₂ films can be both crystalline (for ZnO <1 wt%) and amorphous (for ZnO ≥ 10 wt%) in nature. Atomic force microscopy studies of the as-prepared composite films indicate that the surfaces are fairly smooth with rms roughness varying between 3.07 and 2.04 nm. The average optical transmittance of the as-deposited films in the visible range (400-800 nm), decreases from 90% to 72% for increasing ZnO concentration in the film. The band gap energy (E_g) seems to depend on the amount of ZnO addition, with the maximum obtained at 1 wt% ZnO. Assuming that the interband electron transition is direct, the optical band gap has been found to be in the range 3.24-3.69 eV for as-deposited composite films. The lowest electrical resistivity of 7.6 × 10⁻³ Ω cm has been achieved with the 25 wt% ZnO composite film deposited at 500 °C. The photoluminescence spectrum of the composite films shows a decrease in PL intensity with increasing ZnO concentration.     

Nucleation control for ZnO nanorods grown by catalyst-driven molecular beam epitaxy

We report a study of the annealing temperature and time on Ag catalyst size and density for subsequent growth of ZnO nanorods by catalyst-driven molecular beam epitaxy (MBE). Two different substrates (SiO₂ and SiN_X) for the Ag deposition were used and the thickness of the Ag held constant at 25 Å. Annealing between 600 and 800 °C produced Ag cluster sizes in the range 8-30 nm diameter on SiO₂ and 10-65 nm on SiN_X with a cluster density from 100 to 2500 mm⁻² for SiO₂ and 30 to 1900 mm⁻² for SiN_X. ZnO nanorods grown on these clusters show single-crystal, wurtzite-phase nature and strong band-edge photoluminescence at 380 nm. The nanorods can also be grown selectively on lithographically-patterned dielectric stripes with Ag clusters formed on top by e-beam evaporation and annealing.     

Dual mode emission and harmonic generation in ZnO-CaO-Al2O3: Er nano-composite

Er³⁺ doped ZnO-CaO-Al₂O₃ nano-composite phosphor has been synthesized through combustion method and its emission and harmonic generation properties have been studied. The X-ray diffraction and thermal analysis techniques have been used to prove the dual phase (ZnO and CaO-Al₂O₃) nature of the phosphor. The phosphor has shown up-conversion emission on near-infra-red (976 nm) excitation and down-conversion emission on 355 nm excitation in presence of Er³⁺ and thus behaves as a dual mode phosphor. On excitation with 976 nm diode laser, material shows color tunability (calcination of composite material at different temperatures). Formation of ZnO nanocrystals on heat treatment of as-synthesized sample has shown its characteristic emission at 388 nm and also the energy transfer from ZnO to Er³⁺ ions. The low temperature emission measurements have been carried out and the results have been discussed. Phosphor has shown strong second harmonic generation (SHG) at 532 nm on 1064 nm and at 266 nm on 532 nm excitation.     

Preparation and characterization of bifunctional, Fe3O4/ZnO nanocomposites and their use as photocatalysts

Bifunctional magnetic-optical Fe₃O₄/ZnO nanocomposites with different molar ratio were successfully synthesized by a facile two-step strategy. Compared with the other methods, it was found to be mild, inexpensive, green, convenient and efficient. Fe₃O₄ nanocrystal was used as seed for the deposit and growth of ZnO nanoparticle. A series of the characterizations manifested that the combination of Fe₃O₄ with ZnO nanoparticles was successful. Photocatalytic activity studies confirmed that as-prepared nanocomposites had excellent photodegradating behavior to Methyl Orange (MO) compared to the pure ZnO nanoparticles. The results showed that the degradation percentage of MO was about 93.6% for 1 h when the amount of catalyst was 0.51 g L⁻¹ and initial concentration of MO was 6 × 10⁻⁵ mol L⁻¹ in the pH 7 solution. Moreover, the kinetics of photocatalytic degradation reaction could be expressed by the first-order reaction kinetic model. Furthermore, the Fe₃O₄/ZnO nanocomposites could be also served as convenient recyclable photocatalysts because of their magnetic properties.     

Optical spectroscopy of heavily Ho-doped BaY2F8 crystals

The ultraviolet, visible, and near IR (0.8-2.4 μm) luminescence spectra of BaY₂F₈ single crystals heavily doped with Ho³⁺ ions (10 and 30 mol%) have been investigated at room temperature and 12 K, together with the luminescence decay curves (up to 300 μs) of the visible emission. Excitation in the visible region gives rise to very strong emission bands originating from the first ⁵I₇ level and located around 2070 nm. However the ⁵I₇ emission is not observed upon excitation at wavelengths shorter than 300 nm. The inter-ionic processes are found to shorten the decay times of the levels emitting in the visible region with respect to the corresponding radiative lifetimes.     

Visible photocurrent response of TiO2 anode

The photoelectrochemical response to the electromagnetic radiation over the visible range is particularly sought for from the point of view of the efficiency of hydrogen generation by water photolysis in a photoelectrochemical solar cell, PEC. The PEC used in this work comprises thin film TiO₂ - based photoanode, Pt foil covered with Pt black as a cathode and SCE as a reference electrode, immersed in an electrolyte solution. Titanium dioxide thin films are deposited by means of rf reactive sputtering and modified, when necessary, by Au or Ag ultra-thin overcoatings. Here we show that even unmodified TiO₂ photoanode, shows a photocurrent peak over the visible range of the light spectrum (λ = 500-650 nm). The effect of the surface modification by noble metals and properties of the aqueous electrolyte on the visible photocurrent are studied. The optical spectra indicate an increased absorption due to noble metal deposits at 410 nm for Ag and at 600 nm for Au. In contrast, the photocurrent peak over the visible range (500 nm < λ < 650 nm) changes its symmetry and decreases in intensity with the increasing thickness of noble metals layers. The visible photoresponse is explained in terms of OH formation at the interface between TiO₂ electrode and aqueous electrolyte.     

Studies on fabrication of Ag/Tl2Ba2Ca2Cu3O10/CdSe heterostructures with electrochemical technique

The Ag/Tl₂Ba₂Ca₂Cu₃O₁₀/CdSe heterostructure was fabricated at room temperature by soft electrochemical processing technique for the first time. The formation of the heterostructure with non-diffusive interfaces was confirmed by X-ray diffraction. The crystallite sizes determined for Tl-2223 and CdSe films were 33 nm and 25 nm, respectively. The Tl₂Ba₂Ca₂Cu₃O₁₀ film electrodeposited onto Ag-substrate has shown the superconducting transition temperature T_c at 116.5 K and J_c = 2.1 × 10³ A/cm². These values were found to improve after the deposition of CdSe onto Ag/Tl-2223 films. The effect of red He-Ne laser irradiation on the superconducting properties of heterostructure are studied and discussed at length in this paper.     

Modified texture and high temperature transport properties of doubly substituted BaxAgyCa2.8Co4O9 thermoelectric oxide

Doubly substituted polycrystalline compound bulk samples of Ba_xAg_yCa_2.8Co₄O₉ were prepared via citrate acid sol-gel method followed by spark plasma sintering. The phase composition, orientation, texture and high temperature electrical properties were systematically investigated. The results showed that the orientation and the texture could be modified by altering ratio of Ba to Ag. The resistivity and the Seebeck coefficient of substituted samples were decreased by decreasing Ba/Ag ratio except for that of Ba_0.1Ag_0.1Ca_2.8Co₄O₉ sample with lowest electrical resistivity (7.2 mΩ cm at 973 K), moderately high Seebeck coefficient (172 μV/K at 973 K) and improved power factor (0.42 mW/mK² at 973 K).     

Effect of annealing temperature on structure, magnetic properties and optical characteristics in Zn0.97Cr0.03O nanoparticles

The Cr-doped zinc oxide (Zn_0.97Cr_0.03O) nanoparticles were successfully synthesized by sol-gel method. The relationship between the annealing temperature (400 °C, 450 °C, 500 °C and 600 °C) and the structure, magnetic properties and the optical characteristics of the produced samples was studied. The results indicate that Cr (Cr³⁺) ions at least partially substitute Zn (Zn²⁺) ions successfully. Energy dispersive spectroscopy (EDS) measurement showed the existence of Cr ion in the Cr-doped ZnO. The samples sintered in air under the temperature of 450 °C had single wurtzite ZnO structure with prominent ferromagnetism at room temperature, while in samples sintered in air at 500 °C, a second phase-ZnCr₂O₄ was observed and the samples were not saturated in the field of 10000 Oe. This indicated that they were mixtures of ferromagnetic materials and paramagnetic materials. Compared with the results of the photoluminescence (PL) spectra, it was reasonably concluded that the ferromagnetism observed in the studied samples was originated from the doping of Cr in the lattice of ZnO crystallites.     

Effects of hydrogen flux on the properties of Al-doped ZnO films sputtered in Ar + H2 ambient at low temperature

Al-doped ZnO (AZO) transparent conductive thin films were grown by magnetron sputtering with AZO (98 wt.% ZnO, 2 wt.% Al₂O₃) ceramic target in Ar + H₂ ambient at a relatively low temperature of 100 °C. To investigate the dependence of crystalline and properties of as-grown AZO films on the H₂-flux, X-ray diffraction (XRD), X-ray photoemission spectrometer (XPS), Hall and transmittance spectra measurements were employed to analyze the AZO samples deposited with different H₂-flux. The results indicate that H₂-flux has a considerable influence on the transparent conductive properties of AZO films. The resistivity of 4.15 × 10⁻⁴ Ω cm and the average transmittance of more than 94% in the visible range were obtained with the optimal H₂-flux of 1.0 sccm. Such a low temperature growing method present here may be especially useful for some low-melting point photoelectric devices and substrates.     

Structural, optical and electrical properties of ZnO/Zn2GeO4 porous-like thin film and wires

Zinc oxide/zinc germanium oxide (ZnO/Zn₂GeO₄) porous-like thin film and wires has been fabricated by simple thermal evaporation method at temperature about 1120 °C for 2.5 h. The structural and optical properties of the porous-like-thin film and wires have been investigated by scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDX), X-ray diffraction (XRD) and photoluminescence (PL) spectroscopy. Metal semiconductor metal (MSM) photodetector structure was used to evaluate the electrical characteristics by using current-voltage (I-V) measurements. Room temperature photoluminescence spectrum of the sample shows one prominent ultraviolet peak at 378 nm and a shoulder at 370 nm. In addition, broad visible blue emission peak at wavelength 480 nm and green emission peak at 500 nm are also observed. Strong photoelectric properties of the MSM in the UV demonstrated that the porous-like-thin film and wires contribute to its photosensitivity and therefore making ZnO/Zn₂GeO₄ wires potential photodetector in the shorter wavelength applications.     

A new photoluminescence emission peak of ZnO-SiO2 nanocomposites and its energy transfer to Eu ions

This work reports a new photoluminescence (PL) emission peak at about 402 nm from amorphous ZnO nanoparticles in a silica matrix, and the energy transfer from it to Eu³⁺ ions. The amorphous ZnO-SiO₂ nanocomposites were prepared by the sol-gel method, which is verified by X-ray diffraction (XRD) profiles and FT-IR spectra. The luminescence emission spectra are fitted by four Gauss profiles, two of which at longer wavelength are due to the defects of the material and the others to amorphous ZnO nanoparticles and the Zn-O-Si interface state. With the reduction of Zn/Si ratio and diethanolamine, the relative intensities of visible emission decrease. The weak visible emission is due to the reduction of defects after calcined at high temperature. The new energy state at the Zn-O-Si interface results in strong emission at about 402 nm. When Eu³⁺ ions are co-doped, weak energy transfer from ZnO-SiO₂ nanocomposites to Eu³⁺ emission are observed in the excitation spectra.     

High temperature transport properties of Ag-added (Ca0.975La0.025)3Co4O9 ceramics

Ag-added (Ca_0.975La_0.025)₃Co₄O₉ ceramics were fabricated using spark plasma sintering from the precursor powder synthesized by a polyacrylamide gel method. The results indicated that Ag precipitated as a second phase in Ca₃Co₄O₉ matrix. The addition of Ag was effective in enhancing the electrical conductivity and had a slight effect on Seebeck coefficient. In addition, the temperature dependence of electrical conductivity showed that the hole hopping conduction mechanism was dominant for the Ag-added (Ca_0.975La_0.025)₃Co₄O₉ ceramics. The activation energy remained unchanged with the increasing Ag content. The thermoelectric power factor of Ag-added (Ca_0.975La_0.025)₃Co₄O₉ ceramics reached about 5×10⁻⁴ Wm⁻¹ K⁻² at 700 °C, suggesting a promising thermoelectric oxide candidate at high temperatures.     

Sensitized luminescence through nanoscopic effects of ZnO encapsulated in SiO2:Tb sol gel derived phosphor

Terbium (1 mol%) doped ZnO-SiO₂ binary system was prepared by a sol-gel process. Nanoscopic effects of ZnO on the photoluminescence (PL) and the cathodoluminescence (CL) properties were studied. Defects emission from ZnO nanoparticles was measured at 560 nm and the line emission from Tb³⁺ ions in SiO₂:Tb³⁺ and ZnO-SiO₂:Tb³⁺ with a major peak at 542 nm was measured. The PL excitation wavelength for 542 nm Tb³⁺ emission was measured at ∼320 nm in both SiO₂:Tb³⁺ and ZnO-SiO₂:Tb³⁺. The CL data showed quenched luminescence of the ZnO nanoparticles at 560 nm from a composite of ZnO-SiO₂:Tb³⁺ and a subsequent increase in 542 nm emission from the Tb³⁺ ions. This suggests that energy was transferred from the ZnO nanoparticles to enhance the green emission of the Tb³⁺ ions. The PL and CL properties of ZnO-SiO₂:Tb³⁺ binary system and possible mechanism for energy transfer from the ZnO nanoparticles to Tb³⁺ ions are discussed.     

Preparation and characterization of Zn2SiO4: Mn phosphors with hydrothermal methods

Mn²⁺-doped Zn₂SiO₄ phosphors had been prepared by hydrothermal method in stainless-steel autoclaves. Effects of synthesized methods, reaction temperature, ambience of heat treatment on the structure and the luminescence properties of this silicate were studied with X-ray diffraction apparatus (XRD), transmission electron microscope (TEM), scanning electron microscope (SEM) and fluorescence spectrum. Results show that Zn₂SiO₄ nanocrystalline can be obtained by hydrothermal method at relatively low temperatures. The absorption pattern shows an absorption edge at about 380 nm originated from ZnO crystals and two absorption bands at about 215 and 260 nm. Mn²⁺-doped Zn₂SiO₄ has a luminescence band with the wavelength at about 522 nm under 255 nm excitation, and the luminescent intensity increases after being heat treated.     

Photoluminescence of ZnO nanowires dependent on O2 and Ar annealing

High-purity ZnO nanowires have been synthesized on Si substrates without the presence of a catalyst at 600 °C by a simple thermal vapor technique. Photoluminescence (PL) spectra of the annealed samples at 900 °C under oxygen and argon gases have been investigated. After O₂ or Ar annealing, the PL visible-emission intensity that is related to intrinsic defects (oxygen vacancies) is greatly reduced compared with as-grown ZnO nanowires because the oxygen-gas ions or oxygen interstitials diffuse into the oxygen vacancies during annealing process. The blue-band peak of the O₂- or Ar-annealed ZnO naonowires is also smaller than the green-band peak in the visible broadband because of the reduction of oxygen vacancies. Therefore, the main intrinsic defects (oxygen vacancies) of as-grown ZnO nanowires can be reduced by O₂ or Ar annealing, which is an important procedure for the development of advanced optoelectronic ZnO nanowire devices.     

Synthesis, structural, magnetic and optical properties of nanocrystalline ZnFe2O4

Nanocrystalline zinc ferrite (ZnFe₂O₄) is synthesized by high-energy ball-milling after 12 h from a powders mixture of zinc oxide (ZnO) and hematite (α-Fe₂O₃) with balls to powders mass ratio of 20:1. X-ray diffraction, vibrating sample magnetometer (VSM), the Mössbauer spectrometry and photoluminescence (PL) are used to characterize the samples. Rietveld analysis and VSM measurements show that the powder has an average crystallites size of 10 nm and a ferrimagnetic behavior with a saturation magnetization of 30 emu/g. After annealing at 700 °C, the lattice parameter reduces from 8.448 to 8.427 Å and the sample transforms into a superparamagnetic behavior, which was confirmed as well by the room temperature Mössbauer spectrometry. Different mechanisms to explain the obtained results and the correlation between magnetism and structure are discussed. Finally, the broadband visible emission band is observed in the entire PL spectrum and the estimated energy band gap is about 2.13 eV.     

Spectroscopic investigations of Nd-, Er-, Er/Yb-, and Tm-ions doped SiO2-Al2O3-CaF2-GdF3 glasses

This paper reports on the absorption, visible and near-infrared luminescence properties of Nd³⁺, Er³⁺, Er³⁺/2Yb³⁺, and Tm³⁺ doped oxyfluoride aluminosilicate glasses. From the measured absorption spectra, Judd-Ofelt (J-O) intensity parameters (Ω₂, Ω₄ and Ω₆) have been calculated for all the studied ions. Decay lifetime curves were measured for the visible emissions of Er³⁺ (558 nm, green), and Tm³⁺ (650 and 795 nm), respectively. The near infrared emission spectrum of Nd³⁺ doped glass has shown full width at half maximum (FWHM) around 45 nm (for the ⁴F_3/2→⁴I_9/2 transition), 45 nm (for the ⁴F_3/2→⁴I_11/2 transition), and 60 nm (for the ⁴F_3/2→⁴I_13/2 transition), respectively, with 800 nm laser diode (LD) excitation. For Er³⁺, and Er³⁺/2Yb³⁺ co-doped glasses, the characteristic near infrared emission bands were spectrally centered at 1532 and 1544 nm, respectively, with 980 nm laser diode excitation, exhibiting full width at half maximum around 50 and 90 nm for the erbium ⁴I_13/2→⁴I_15/2 transition. The measured maximum decay times of ⁴I_13/2→⁴I_15/2 transition (at wavelength 1532 and 1544 nm) are about 5.280 and 5.719 ms for 1Er³⁺ and 1Er³⁺/2Yb³⁺ (mol%) co-doped glasses, respectively. The maximum stimulated emission cross sections for ⁴I_13/2→⁴I_15/2 transition of Er³⁺ and Er³⁺/Yb³⁺ are 10.81×10⁻²¹ and 5.723×10^-21 cm². These glasses with better thermal stability, bright visible emissions and broad near-infrared emissions should have potential applications in broadly tunable laser sources, interesting optical luminescent materials and broadband optical amplification at low-loss telecommunication windows.     

Electrochemical synthesis and optical properties of ZnO thin film on In2O3:Sn (ITO)-coated glass

ZnO thin films were electrochemically deposited onto the ITO-coated glass substrate from an electrolyte consisted of 0.1 M Zn(NO₃)₂ aqueous solution at 65 ± 1 °C. A compact ZnO film with (0 0 2) preferred orientation was obtained at the applied potential of −1.3 V for 1200 s. It was also found that the morphology of the ZnO films grown at the potential of −1.3 V was characterized of single or coalescent hexagonal platelets. However, the ZnO crystals grown at the potential of −2.0 V was changed to be a bimodal size distribution. The band gap energy of the as deposited ZnO films, about 3.5 eV, was independent of both the applied potential and the deposition time, respectively. The minor amount of Zn(OH)₂ might be co-deposited with the formation of ZnO revealed by the FT-IR spectroscopy. Three strategies to improve the ZnO crystal quality based on the photoluminescence properties were proposed in the paper, which were (a) adopting the lower deposition potential, (b) increasing the deposition time at a certain potential, and (c) annealing after as-deposition, respectively.     

Effect of doping on the luminescence properties of Li2B4O7

In this work, we have investigated the influence of doping agents on the luminescence properties of multiply doped Li₂B₄O₇ and the temperature lag between TSL materials and the heating element. The results of thermoluminescence studies show that the Ag doping leads to the appearance of a new glow curve peak at 165 °C and the increasing sensitivity of Li₂B₄O₇:Cu,Ag,P is correlated with copper and phosphate concentrations. Under the excitation at 245 nm the emission spectra show maxima at 365 and 450 nm in the ceramic, crystal and glass. The low energy shift in the latter system might be related to the local structural distortion in the glass around Cu⁺ ions.