Influence of porosity on laser damage threshold of sol–gel ZrO2 and SiO2 monolayer films

Monolayer ZrO₂ sol–gel and physical vapor deposition (PVD) films were prepared by spin method and electron beam evaporation method, respectively. Monolayer sol–gel SiO₂ films were prepared with the dip-coating method from acid and base catalyzed SiO₂ sols, respectively. Some of the SiO₂ base films were subsequently treated in saturated ammonia gas for 20 h. The laser induced damage threshold (LIDT) of each film was measured. Properties of the films were analyzed by using Stanford photo-thermal solutions (SPTSs), ellipsometer, atomic force microscopy (AFM) and optical microscopy. The experimental results showed that porous ratio is an essential factor to decide the LIDT for sol–gel films, which benefits the pressure exerted on the film or substrate by the moving particle to dissipate. The films with lower thermal absorption and higher porous ratio have higher LIDT.     

Low-temperature photoluminescence spectra of CdO–In2O3 thin films prepared by sol–gel

(CdO)_1?x–(InO_3/2)_x thin films were deposited on glass substrates by the sol–gel method. The precursor solutions for the mixed oxide films were obtained from the mixture of the precursor solutions for CdO and In₂O₃ prepared separately. The investigated In atomic concentrations in the solution, x, were 0.0, 0.16, 0.33, 0.50, 0.67, 0.84, and 1. X-ray diffraction measurements showed that the films were mainly constituted of CdO, In₂O₃, and CdIn₂O₄. CdO and In₂O₃ were obtained for x=0 and 1, respectively. For x=0.67, which is the stoichiometric composition of the CdIn₂O₄ compound, only this oxide was formed. CdO and CdIn₂O₄ crystals were obtained in the Cd-rich region, whereas In₂O₃ and CdIn₂O₄ crystals were formed in the In-rich region. The PL spectra at 15 K for CdO showed the presence of two main emission bands at energies close to 2.2 and 3.0 eV. A blue-shift of these bands took place for increasing In concentration, which is related to the increase in the band gap energy of the mixed system in going from CdO, with a band gap energy of 2.46 eV, to CdIn₂O₄, with 3.2 eV, to In₂O₃, with 3.6 eV.     

Ion-irradiation enhanced epitaxial growth of sol–gel TiO2 films

We report the epitaxial growth of sol–gel TiO₂ films by using ion-irradiation enhanced synthesis. Our present study shows that the ion-beam process can provide highly crystalline TiO₂ even at 350°C. Nuclear energy deposition at amorphous/crystalline interface plays a dominant role in the epitaxial growth of the films at the reduced temperature via a defect-migration mechanism. In addition, the ion irradiation allows for increasing the film density by balancing the crystallization rate and the escape rate of organic components.     

Study of the formation of Co3O4 thin films using sol–gel method

Sol–gel derived coatings containing cobalt have been analyzed using impedance and reflection measurements. It is found that during the thermal treatments in air at temperatures in the range of 35–400 °C, cobalt migrates to the front surface of the coating where it is oxidized by the atmospheric oxygen and forms a top layer rich in nanocrystalline Co₃O₄. In samples heated above 260 °C, the current flows entirely through this top layer because it has higher conductivity than the rest of the coating. For these samples, the impedance spectra show two semicircles, related with the electrical properties of grain and grain boundaries of the cobalt oxide layer. Using the brick model, the grain boundary volume fraction was calculated as a function of the heating temperature.     

Microstructure and electro-optical properties of sol–gel derived Cd-doped ZnO films

The microstructure, and the electrical and optical properties of undoped zinc oxide (ZnO) and cadmium-doped ZnO (CZO) films deposited by a sol–gel method have been investigated. The films have a polycrystalline structure with hexagonal wurtzite ZnO. Scanning electron microscopy (SEM) images indicated that the films have a wrinkle network with uniform size distributions. The elemental analyses of the CZO films were carried out by energy dispersive X-ray analysis. The fundamental absorption edge changed with doping. The optical band gap of the films decreased with Cd dopant. The optical constants of the films such as refractive index, extinction coefficient and dielectric constants changed with Cd dopant. A two-probe method was used to investigate the electrical properties, and the effect of Cd content on the electrical properties was investigated. The electrical conductivity of the films was improved by incorporation of Cd in the ZnO film.     

Thermoluminescence of Al2O3:Cr3+ films synthesized by the nonaqueous sol–gel method

The thermoluminescence (TL) properties of Al₂O₃:Cr³⁺ thin films prepared by the nonaqueous sol–gel method were evaluated. The obtained thin films were characterized by scanning electron microscope and energy dispersive spectrometry. They were irradiated with ⁶⁰Co gamma rays of the different doses. TL glow curves exhibited two peaks centered at 197°C and 322°C.The heights of peaks were found to be sensitive to exposures of ionizing irradiation and the integral area of the TL signals had a linear response in the dose range of 5–60 Gy.This remarkable result suggests that Al₂O₃:Cr³⁺ films might potentially be used for radiation dosimetry.     

Experimental research of laser-induced damage of the monolayer ZrO2 PVD and sol–gel films

Monolayer zirconia physical vapor deposition (PVD) and sol–gel films on K9 glass substrates were prepared by electron beam evaporation and spin coating methods, respectively. The laser-induced damage threshold (LIDT) of each film was measured. Properties of the films were analyzed using Stanford photo-thermal solutions (SPTS), ellipsometry, atomic force microscopy (AFM) and optical microscopy to study the damage mechanism of films under laser irradiation. The experimental results showed that, compared with the monolayer zirconia sol–gel film, the monolayer zirconia PVD film had larger absorption and smaller porous ratio, and that it had smaller LIDT. The different damage morphologies of films were influenced by their different absorption and microstructure characteristics. The zirconia sol–gel film is more suitable for applications involving high-power lasers.     

Structural,electrical and optical properties of sol–gel AZO thin films

Transparent conductive Al-doped zinc oxide (AZO) thin films were prepared by a sol–gel method and their structural, electrical and optical properties were systematically investigated. A minimum resistivity of 4.2 × 10⁻³ Ω cm was obtained for the 650 °C-annealed films doped with 1.0 at.% Al. All films had the preferential c-axis oriented texture according to the X-ray diffraction (XRD) results. Optical transmittance spectra of the films showed a high transmittance of over 85% in the visible region and the optical band gap of the AZO films broadened with increasing doping concentration.     

Structure and site selective luminescence of sol–gel derived Eu:Sr2SiO4

Strontium silicate (Sr₂SiO₄) samples doped with varying Eu³⁺content were prepared via sol–gel route and characterized by X-ray diffraction (XRD), atomic force microscopy (AFM), scanning electron microscopy (SEM), dynamic light scattering (DLS) and photoluminescence (PL) techniques. The synthesis temperature could be brought down to 600 °C for formation of a singe phase sample. The concentration of the dopant ion and the temperature of annealing were optimized for maximum PL intensity. The critical energy-transfer distance for the Eu³⁺ ions was evaluated based on which the quenching mechanism was verified to be a multipole–multipole interaction. Based on the time-resolved emission data (TRES), it was inferred that, two different types of Eu³⁺ ions were present in the matrix. The first type was a long lived species (τ=4.7 ms) present at 10-coordinated ‘Sr’sites and the other was a short lived species (τ=1.2 ms) present at the 9-coordinated ‘Sr’sites which gets selectively excited at 296 nm. Judd–Ofelt (J–O) intensity parameters for both the species were evaluated. The trend observed for the two species in the J–O parameters, Ω₂ and Ω₄ were different confirming their existence in two different environments. The color coordinates of the system were evaluated and plotted on a CIE index diagram. Commercial utility of the phosphor was investigated by comparing it with commercial red phosphor.     

The broadband NIR emission properties of Bi doped La2O3–Al2O3–SiO2 glass

Bi₂O₃ doped 65SiO₂–20Al₂O₃–15La₂O₃ (in mole%) glasses were prepared by the traditional melting–quenching method. The spectroscopic properties and mechanism of NIR broadband emission in these glasses were investigated in this work. Three excitation wavelengths of 500, 700 and 800 nm were used to test emission spectra. The emission band under 500 nm excitation can be regarded as combination of emission bands under 700 and 800 nm excitation. 2.0 mole% is found to be the optimal Bi₂O₃ doping level in this glass. Under 500 nm excitation its emission peak, FWHM and lifetime of emission band are 1160 nm, 300 nm and 569 μs, respectively. The longest fluorescent lifetime reaches 620 μs under 700 nm excitation. The valence state of Bi in these glasses is suggested to be lower than +3 by X-ray photoelectron spectroscopy. With the help of energy matching, we infer that both Bi⁰ and Bi⁺ centers are responsible for the NIR fluorescence of Bi₂O₃ doped 65SiO₂–20Al₂O₃–15La₂O₃ glass.     

Nanostructures and luminescence properties of porous ZnO thin films prepared by sol–gel process

ZnO thin films containing nano-sized pores were synthesized on solid substrates through a sol–gel process by accommodating cetyl-trimethyl-ammonium bromide (CTAB) as an organic template in the precursor solution. By X-ray diffraction the resultant ZnO films were found to possess ordered pore arrays forming lamellar structure with the spacing between two adjacent pores being ∼3.0 nm. Photoluminescence measurements indicated that the surfactants effectively passivated the surface defects of the ZnO films responsible for the green emission. Al doping was found to improve not only the lamellar structure of the pore arrays but also the near-band-gap emission intensity while the suppression effect of CTAB on the green emission remained undisturbed. With a proper control of doping level, the optical property as well as the structural integrity can be tailored to augment the potential of ZnO films for the optoelectronics and sensor applications.     

Electrical and optical properties of Sb-doped ZnO thin films synthesized by sol–gel method

Sb-doped ZnO thin films with different values of Sb content （from 0 to 1.1 at.%） are deposited by the sol-gel dip- coating method under different sol concentrations. The effects of Sb-doping content, sol concentration, and annealing ambient on the structural, optical, and electrical properties of ZnO films are investigated. The results of the X-ray diffraction and ultraviolet-visible spectroscopy （UV-VIS） spectrophotometer indicate that each of all the films retains the wurtzite ZnO structure and possesses a preferred orientation along the c axis, with high transmittance （〉 90%） in the visible range. The Hall effect measurements show that the vacuum annealed thin films synthesized in the sol concentration of 0.75 mol/L each have an adjustable n-type electrical conductivity by varying Sb-doping density, and the photoluminescence （PL） spectra revealed that the defect emission （around 450 nm） is predominant. However, the thin films prepared by the sol with a concentration of 0.25 mol/L, despite their poor conductivity, have priority in ultraviolet emission, and the PL peak position shows first a blue-shift and then a red-shift with the increase of the Sb doping content.     

TEM characterization of organic nanocrystals grown in sol–gel thin films

The tetracene molecule (2,3-benzanthracene, C₈H₁₂) was used to synthesize nanocrystals grown in sol–gel thin films, ranging from 10 to 100 nm of diameter. This confined nucleation and growth was compared to microcrystallizations of the same molecule in free solution. Transmission electron microscopy (TEM) was used to characterize these two kinds of tetracene crystals. The observation was performed under low-dose illumination to avoid amorphization of the samples during electron irradiation. Spatial confinement and size distribution of micro- and nanocrystals were compared. Using electron microdiffraction and diffraction patterns simulations, we showed that free microcrystals and nanocrystals confined in gel glasses exhibit the same triclinic structure. In addition, time-resolved spectroscopy was used to record fluorescence decays, showing a monoexponential fluorescence decay for nanocrystals while microcrystals exhibit a multiexponential decay. The simple signature of nanocrystals luminescence is promising for the future development of chemical or biological sensors.     

Synthesis and characterization of nanostructured strontium hexaferrite thin films by the sol–gel method

Nanostructured single phase strontium hexaferrite, SrFe₁₂O₁₉, thin films have been synthesized on the (100) silicon substrate using a spin coating sol–gel process. The thin films with various Fe/Sr molar ratios of 8–12 were calcined at different temperatures from 500 to 900 °C. The composition, microstructure and magnetic properties of the SrFe₁₂O₁₉ thin films were characterized using Fourier transform infrared spectroscopy, differential thermal analysis, thermogravimetry, X-ray diffraction, electron microscopy and vibrating sample magnetometer. The results showed that the optimum molar ratio for Fe/Sr was 10 at which the lowest calcination temperature to obtain the single phase strontium hexaferrite thin film was 800 °C. The magnetic measurements revealed that the sample with Fe/Sr molar ratio of 10, exhibited higher saturation magnetization (267.5 emu/cm³) and coercivity (4290 Oe) in comparison with those synthesized under other Fe/Sr molar ratios.     

Study of NiCuZn ferrite powders and films prepared by sol gel method

This paper reports that a series of NiCuZn ferrite powders and films are prepared by using sol-gel method.The effects of raw material composition and the calcinate temperature on magnetic properties of them are investigated.The NiCuZn ferrite powders are prepared by the self-propagating high-temperature synthesis method and subsequently heated at 700 C～1000 C.The results show that NiCuZn ferrite powders with single spinel phase can be formed after heat-treating at 750 C.Powders obtained from Ni 0.4 Cu 0.2 Zn 0.4 Fe 1.9 O 4 gel have better magnetic properties than those from gels with other composition.After heat-treating at 900 C for 3 h,coercivity H c and saturation magnetization M s are 9.7 Oe (1 Oe=80 A/m) and 72.4 emu/g,respectively.Different from the powders,NiCuZn films produced on Si (100) from the Ni 0.4 Cu 0.2 Zn 0.4 Fe 2 O 4 gel formed at room temperature possess high properties.When heat-treating condition is around 600 C for 6 min,samples with low H c and high M s will be obtained.The minimal H c is 16.7 Oe and M s is about 300 emu/cm 3.In comparison with the films prepared through long-time heat treating,the films prepared through short heat-treating time exhibits better soft magnetic properties.     

Study of structural and magnetic properties of superparamagnetic Fe3O4/SiO2 core–shell nanocomposites synthesized with hydrophilic citrate-modified Fe3O4 seeds via a sol–gel approach

This paper describes a simple way for the coating of magnetite nanoparticles (MNPs) with amorphous silica. First, MNPs were synthesized by controlled co-precipitation technique under N₂ gas and then their surface was modified with trisodium citrate in order to achieve particles with improved dispersibility. Afterward, magnetite-silica core/shell nanocomposites were prepared by a sol–gel approach, using magnetic fluid including electrostatically stabilized MNPs as seeds. The prepared samples were characterized by means of X-ray diffraction (XRD), transmission electron microscopy (TEM), Fourier transform infrared (FT-IR) spectroscopy, zeta potential analysis and vibrating sample magnetometer (VSM) in order to study their structural and magnetic properties. FT-IR and XRD results imply that resultant nanocomposites are consisted of two compounds; Fe₃O₄ and SiO₂ and TEM images confirm formation of their core/shell structure. TEM images also show increase in silica shell thickness from ∼5 to ∼24 nm with increase in amount of tetraethyl orthosilicate (TEOS) used during the coating process from 0.1 to 0.3 mL. Magnetic studies indicate that Fe₃O₄ nanoparticles remain superparamagnetic after coating with silica although their M_s values are significantly less than pristine MNPs. These core/shell nanocomposites offer a high potential for different biomedical applications due to having superparamagnetic property of magnetite and unique properties of silica.     

Synthesis and photoluminescence of core–shell structured spherical SiO2@YPO4:Tb3+ phosphors via sol–gel process

Monodispersed SiO₂@YPO₄:Tb³⁺ core–shell submicrospheres were prepared through a simply homogeneous sol–gel method. The resulted SiO₂@YPO₄:Tb³⁺ core–shell particles were characterized by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), field emission scanning electron microscopy (FESEM), energy-dispersive X-ray spectra (EDS), transmission electron microscopy (TEM), photoluminescence spectra (PL) and kinetic decays. The XRD results demonstrate that the YPO₄:Tb³⁺ layers begin to crystallize on the SiO₂ spheres after annealing at 500 °C and the crystallinity increases with raising the annealing temperature. The FTIR spectra show that the YPO₄:Tb³⁺ shell has linked to the silica surface through forming a Si–O–Y bond. SEM and TEM analysis indicate that SiO₂@YPO₄:Tb³⁺ core–shell submicrospheres have the regular microstructures and uniform size distributions. The emission spectra of the obtained submicrospheres are dominated by ⁵D₄–⁷F₅ transition of Tb³⁺ (545 nm, green), and the emission intensities of Tb³⁺ increase with increasing the annealing temperatures and the number of coating cycles. The optimum concentration for Tb³⁺ was determined to be 5 mol % of Y³⁺ in YPO₄ host.     

Temperature dependent structural and optical properties of nanocrystallineCdO thin films deposited by sol–gel process

Nanocrystallites of cadmium oxide (CdO) thin films were deposited by sol–gel dip coating technique on glass and Si substrates. XRD and TEM diffraction patterns confirmed the nanocrystalline cubic CdO phase formation. TEM micrograph of the film revealed the manifestation of nano CdO phase with average particle size lying in the range 1.6–9.3 nm. UV–Vis spectrophotometric measurement showed high transparency (nearly 75% in the wavelength range 500–800 nm) of the film with a direct allowed bandgap lying in the range 2.86–3.69 eV. Particle size has also been calculated from the shift of bandgap with that of bulk value for the films for which the particles sizes are comparable to Bohr exitonic radius. The particle size increases with the increase in annealing temperature and also the intensity of XRD peaks increases which implies that better crystallinity takes place at higher temperature.This revised version was published online in August 2005 with a corrected issue number.