制备条件对铝掺杂氧化锌(AZO)薄膜结构和电学性质的影响

本文利用溶胶-凝胶法在玻璃基底上制备得到了AZO透明导电薄膜,就两种不同的热处理-退火方式对薄膜的结构与性质的影响做了比较,研究了掺杂浓度、退火温度对薄膜结构及性质的影响规律.结果表明,高温、分层退火、铝掺杂均有利于生成结晶度高、具有C轴优先取向的AZO薄膜;高温和分层退火有利于晶粒长大,相反铝掺杂却有碍晶粒长大;薄膜的电学性质随退火温度和铝掺杂量的变化呈现规律的变化.通过分析AZO薄膜内的晶体生长过程,本文认为主要是制备条件和AZO晶体的晶面习性导致了薄膜的结晶度、晶体生长取向性和晶粒尺寸等方面的差异.     

Structural and magnetic properties of nano-crystalline FeCoNiN thin films

Iron cobalt nickel nitride (FeCoNiN) thin films are prepared by sol-gel spin coating route. The structural, magnetic and surface properties of the thin films are evaluated. The crystalline nature of thin films was enhanced upon annealing, leading to increased crystallite size. The X-ray diffraction shows mixed phases with crystallite size in the range of 20–26.93 nm. Thin films show ferromagnetism at room temperature. Coercivity and saturation magnetization are in the range of 642–716 Oe and 2.5–7.5 emu/cm³ respectively. Both coercivity and saturation magnetization increased with annealing of thin films. Magnetic properties are related to the crystallinity of thin films. The increase in crystallite size results into an increase of magnetic properties. Rectangular shaped particles are seen on the surface of thin films. The same type of grains can be seen on the surface of thin films which confirmed the formation of FeCoNiN as predicted by XRD. These novel thin films might be used in memory devices and optoelectronic applications.     

Synthesis and Characterization of CdSe Nanocrystals Capped by CdS

CdSe semiconductor nanocrystals capped by CdS were synthesized in the aqueous solution with 2-mercaptoethanol as the stabilizer. The CdS capping with a higher band-gap than that of the core crystallite has successfully eliminated the surface traps. Optical absorption and fluorescence emission spectra were used to probe the effect of CdS passivation on the electronic structure of the nanocrystals. The composite CdSe/CdS nanocrystals exhibit strong, narrow(FWHM≤40 nm) and stable band-edge photoluminescence. X-ray powder diffraction, transmission electron microscopy and X-ray photoelectron spectroscopy were used to analyze the composite nanocrystals and determine their average size, size distribution, shape, internal structure and elemental composition.     

Strength of interactions between immobilized dye molecules and sol-gel matrices

In this paper we present a new theory to re-examine the immobilization technique of dye doped sol-gel films, define the strength and types of possible bonds between the immobilized molecule and sol-gel glass, and show that the immobilized molecule is not free inside the pores as was previously thought. Immobilizing three different pH sensitive dyes with different size and functional groups inside the same sol-gel films revealed important information about the nature of the interaction between the doped molecule and the sol-gel matrix. The samples were characterized by means of ultraviolet-visible spectrophotometer (UV-VIS), thermal gravimetric analysis (TGA), mercury porosimetry (MP), nuclear magnetic resonance spectroscopy ((29)Si NMR) and field-emission environmental scanning electron microscopy (ESEM-FEG). It was found that the doped molecule itself has a great effect on the strength and types of the bonds. A number of factors were identified, such as number and types of the functional groups, overall charge, size, pK(a) and number of the silanol groups which surround the immobilized molecule. These results were confirmed by the successful immobilization of bromocresol green (BCG) after a completely polymerized sol-gel was made. The sol-gel consisted of 50% tetraethoxysilane (TEOS) and 50% methyltriethoxysilane (MTEOS) (w/w). Moreover, the effect of the immobilized molecule on the structure of the sol-gel was studied by means of a leaky waveguide (LW) mode for doped films made before and after polymerization of the sol-gel.     

Synthesis of cadmium sulphide in pure and mixed Langmuir-Blodgett films of n -octadecylsuccinic acid

Cadmium sulphide (CdS) nanoparticles were grown by the reaction of sodium sulphide (Na₂S) with Langmuir-Blodgett (LB) films of cadmium salts ofn-octadecylsuccinic acid (ODSU) and with LB films of ODSU in mixtures of octadecylamine and octadecyl alcohol. The results indicate that heterogeneous nucleation and aggregation in the pure ODSU LB films due to processes like Ostwald ripening are destabilized by the presence of the long-chain amine and alcohol in mixed systems. CdS nanoparticles in the LB films were monitored by UV-visible absorption spectra, which allow an estimation of the size of the particles. The morphology, size and nature of the nanocrystallites formed depend on whether the sulphidation was done on the pure film or in the mixed films. It is seen that particles of size around 1.6 nm were formed in ODSU/octadecylalcohol and ODSU/ octadecylamine mixed LB films while in pure ODSU films the size was about 2.7 nm. These films showed typical needle-shaped structures, as observed by the optical microscopic technique. Mean size and morphology were confirmed by transmission and scanning electron microscopy, while selective area electron diffraction patterns showed six-fold symmetry and indicated that the CdS crystals grow epitaxially with respect to the monolayer. Further, the crystallisation enhanced in the mixed LB films showed a characteristic zinc oxide (Wurtzite) structure compared with the pure ODSU matrix.     

Reactor neutrons irradiation effect on the photocatalytic activity of SnO<Subscript>2</Subscript> thin films

SnO₂ thin films synthesized by sol-gel are irradiated with reactor neutrons up to fast neutron fluence of 9.6 × 10¹⁷ neutrons cm^–2 at 40°C. The influence of defects generated by neutrons irradiation, through the properties modification, on the photo-catalytic activity of SnO₂ films is investigated. It is found that the photoactivity of the irradiated films is enhanced after reactor neutrons irradiation. An improvement of 41% is observed for the sample irradiated at a neutron fluence of 9.6 × 10¹⁷ neutrons cm^–2. This is attributed to several parameters modified by the reactor neutron irradiation principally the crystallite size and space charge region which are closely related to the photocatalytic performance.     

Low-temperature preparation of nanocrystalline anatase films through a sol-gel route

Nanocrystalline anatase (TiO₂) films were prepared at very low temperature through a sol-gel route using titanium isopropoxide and hydrogen peroxide in ethanol. Crystallization occurred after film deposition at 35°C in an atmosphere saturated with water vapor. Both thin and thick films of nanocrystalline anatase were prepared. Observed particle size in crystallized films is approximately 20–40 nm as measured with AFM. No residual organic material was apparent through FTIR after crystallization occurred. Dynamic light scattering studies performed on this system indicate that particle size measured in solution is strongly dependent on the amount of agitation samples received prior to measurement.     

Effect of alumina incorporation on restricting grain growth of nanocrystalline tin(IV) oxide

In this project, nanocrystalline SnO₂ powders were successfully prepared by (a) citrate sol-gel and (b) direct precipitation methods. Powders were characterized using thermal analysis techniques (DTA-TG-DSC), X-ray powder Diffraction (XRD), surface area (BET) and electrical conductivity measurements. XRD patterns showed the presence of the cassiterite structure. SnO₂ particles, prepared through sol-gel method exhibit crystallite sizes in the range from 3.1 to 22.3 nm when the gel is heat treated at different temperatures up to 900°C. SnO₂ nanocrystallites prepared by the precipitation method are comparatively larger in size. The higher specific surface area was obtained for the powder prepared using sol-gel method and the obtained average grain size (d) is relatively large compared with that of the average crystallite size. The powders show a semiconducting behavior with increasing temperature. The higher conductivity obtained for SnO₂ prepared by sol-gel method can be attributed to their smaller average crystallite size. XRD of alumina doped powder exhibits finer particles than pure SnO₂. TEM images showed that the particles are spherical in shape and consist of a core of SnO₂ surrounded by a coating of alumina. The calculated surface area was found to decrease with temperature increases. Due to the effective role of Al₂O₃ additive as a grain growth inhibitor for the matrix grains, the observed surface area for the coated materials are predominantly higher than for the uncoated materials.      

Study on the Superhydrophilicity of the SiO2-TiO2 Thin Films Prepared by Sol-Gel Method at Room Temperature

Nanoscale SiO₂-TiO₂ composite thin films with the thickness of about 100 nm were prepared by sol-gel method at room temperature in air. The chemical states of the elements on the surface and near the surface were measured by XPS. The results showed that the Ti on/near the surface of the thin films existed not only as TiO₂ but also as Ti₂O₃. Part of the TiO₂ was changed to Ti₂O₃ after UV irradiation. The crystalline structure of the TiO₂ in the SiO₂-TiO₂ thin films was anatase with the crystallite size of 14–20 nm. It was found that the thin film prepared at room temperature in air has good superhydrophilic property and has strong adherence to the substrate.     

A Microstructural Zone Model for the Morphology of Sol-Gel Coatings

The thickness and the morphology of dip-coated single sol-gel layers is easily controlled by varying the sol compositions and the deposition parameters. A thorough study of the microstructure of transparent conducting ZnO:Al coatings deposited on fused silica substrates using X-ray diffraction, X-ray reflectometry and transmission electron microscopy cross-sections as well as of In₂O₃:Sn, SnO₂:Sb, ZnO and TiO₂ coatings reported in the literature shows that three basic morphologies can be observed: granular, layered and columnar. In multilayer systems they were found to depend essentially on the single layer thickness (SLT) and on the crystallite size determined from the data of thick films, a parameter called the “intrinsic crystallite size (ICS)”. All the results so far analysed are in agreement with a 3-zone model when ICS is plotted against SLT or in a more refined version when q = ICS/SLT is plotted against the homologous temperature T _sintering/T _melting. Comparison with the Movchan-Demchishin and Polley-Carter models proposed for PVD and CVD coatings, respectively, is presented.     

Sol-Gel Deposited Sb-Doped Tin Oxide Films

The structural, electrical and optical properties of single sol-gel derived antimony-doped tin oxide (ATO) films sintered at 550°C have been measured. The reproducibility of both the preparation and the characterization procedures have been tested by a round-robin test involving eight laboratories within a Concerted European Action (CEA) project. The resistivity measured as a function of Sb content has been obtained by electric and reflectance and transmission measurements. Their differences are discussed in terms of structural and grain boundary effects. An increase of Sb content results in a decrease of the crystallite size (7.0 to 5.4 nm) and a greater influence of the grain boundary.     

Low Dielectric Constant Organosilicate Films Prepared by Sol-Gel and Templating Methods

Low dielectric constant organosilicate films with controllable microstructure have been successfully synthesized by multiple-step sol-gel process and templating method, which are the two basic methods to establish porous network in the films. Ultra-low dielectric constant (k) of around 2.0 can be achieved for both films. The microstructure such as porosity, pore interconnection and pore size of the two types of the films have been studied and compared. It has been found that the sol-gel films have a higher level of porosity comparing to the templating films to obtain the same k value. The sol-gel film has a majority of closed pores with pore size around 5 nm. The templating film has a closed pore structure with pore size around 10 nm. Preliminary results present a very positive prospective for intermetal dielectric applications.     

100 keV H+ ion irradiation of as‐deposited Al‐doped ZnO thin films: An interest in tailoring surface morphology for sensor applications

We report the influence of 100 keV H⁺ ion beam irradiation on the surface morphology, crystalline structure, and transport properties of as‐deposited Al‐doped ZnO (Al:ZnO) thin films. The films were deposited on silicon (Si) substrate by using DC sputtering technique. The ion irradiation was carried out at various fluences ranging from 1.0 × 10¹² to 3.0 × 10¹⁴ ions/cm². The virgin and ion‐irradiated films were characterized by X‐ray diffraction, Raman spectroscopy, atomic force microscopy, and Hall probe measurements. Using X‐ray diffraction spectra, 5 points Williamson‐Hall plots were drawn to deduce the crystallite site and strain in Al:ZnO films. The analysis of the measurements shows that the films are almost radiation resistant in the structural deformation under chosen irradiation conditions. With beam irradiation, the transport properties of the films are also preserved (do not vary orders of magnitude). However, the surface roughness and the crystallite size, which are crucial parameters of the ZnO film as a gas sensor, are at variation with the ion fluence. As ion fluence increases, the root‐mean‐square surface roughness oscillates and the surface undergoes for smoothening with irradiation at chosen highest fluence. The crystallite size decreases initially, increases for intermediate fluences, and drops almost to the value of the pristine film at highest fluence. In the paper, these interesting experimental results are discussed in correlations with ion‐matter interactions especially energy losses by the ion beam in the material.     

Patterned Deposition of Sol-Gel Thin Films Using an Airbrush

ABSTRACT

In this article, we present a method to pattern glass substrates with sol-gel derived thin films. This method is based on the aerosol deposition of sol-gel precursor solutions using an inexpensive, commercially available airbrush. The technique was demonstrated using Cy5-doped sol-gel thin films for the creation of wavelength conversion devices. The films deposited were mechanically and chemically rigid, and patterns could be achieved with a resolution limit of approximately 250 μm. Constructing channel waveguides was also attempted using both zirconium- and titanium-based sol-gel thin films. Deposited thin films of these materials showed graininess that limited the ability to couple light into the films and increased the observed scatter. However, light was successfully coupled into the titanium-based sol-gel film using small lens-like structures created on the glass surface.     

Synthesis and Characterization of Nano-Crystalline Fluorine-Doped Tin Oxide Thin Films by Sol-Gel Method

Thin films of fluorine-doped tin-oxide (FTO) were prepared by sol-gel dip-coating technique. Stannous chloride (SnCl₂2H₂O) and hydrogen fluoride (HF) were mixed with isopropyl alcohol to serve as source solution. X-ray diffraction (XRD) spectrum showed all the peaks of the crystalline SnO₂. Analysis of XRD spectrum showed the particle size to be nearly 6 nm, which indicated the nanocrystalline structure of the films. Strain calculation by integral breadth (IB) method from XRD data showed a value of 0.010. UV-Visible spectrophotometric measurement showed high transparency of the films in the visible region and the band gap was calculated to be 3.34 eV. The room temperature resistivity of the films were of the order of 1 cm. Fluorine concentration in the films was determined from energy dispersive X-ray (EDX) study. Current-voltage (I-V) characteristics at high temperatures showed the Poole-Frenkel effect of thermionic emission. SEM study indicated the existence of fine grains in the film. FT-IR spectroscopy showed strong Sn—O and Sn—O—Sn bonding.     

Control of Semiconductor Particle Size in Sol-Gel Thin Films

Thin silica and silica-titania films containing CdS and PbS quantum size particles were obtained by separate preparation of the matrix and the colloidal sols and successive mixing. Sulfide particles were obtained by reaction of metal acetates with thioacetamide and control of particle size was achieved by surface capping agents. Powders and thin films deposited on soda-lime slides were prepared and characterized by XRD. Absorption spectra were recorded on films. The nonlinear refractive index was measured by anm-line technique on a CdS-doped sample. The nonlinear effect was found to be reversible and an ₂ value of −3 10⁻⁹ cm²/kW was measured.     

New elaboration of Na2O-B2O3-SiO2 glass doped with CdS nanocrystals from gel formed in aqueous solution

A new route for preparing a CdS doped sodium borosilicate glass from a gel formed in an aqueous solution is described. This elaboration process allows the preparation of a gel which starts densifying at 400°C just after the Cd sulphurizing process ensuring the protection of crystallites from oxidation. The densification of the matrix is completed at the fusion temperature (730°C), which is low enough to reduce the coalescence of the crystallites. Microstructural and optical characterization of the CdS doped glasses indicate that the crystallite size depends upon the Cd concentration. A model to calculate the crystallite size from optical absorption spectra is proposed. It indicates that the average sizes of crystallites range from 11 nm for a concentration of 0.03 mol% Cd to 3.7 nm for 0.016 mol% Cd.     

The diffusion of Pt in BST films on Pt/Ti/SiO2/Si substrate by sol-gel method

Barium strontium titanate (Ba_0.65Sr_0.35TiO₃) ferroelectric thin films have been prepared by sol-gel method on Pt/Ti/SiO₂/Si substrate. The X-ray diffraction (XRD) pattern indicated that the films were a polycrystalline perovskite structure and the atomic force microscope (AFM) image showed that the crystallite size and the root mean square roughness (RMS) were 90 nm and 3.6 nm, respectively. The X-ray photoelectron spectrum (XPS) images showed that Pt consisting in BST thin films was the metallic state, and the Auger electron spectroscopy (AES) analysed the Pt concentration in different depth profiles of BST thin films. The result displayed that the Pt diffusion in BST thin film is divided into two regions: near the BST/Pt interface, the diffusion type was volume diffusion, and far from the interface correspondingly, the diffusion type became grain boundary diffusion. In this paper, the previous researcher’s result was used to verify our conclusion.     

Optical and electrical properties of barium titanate-hydroxyapatite composite screen-printed thick films

In this paper we will study the effect of the presence of hydroxyapatite (HA—Ca₁₀(PO₄)₆(OH)₂) on the dielectric permittivity and losses of the barium titanate (BTO—BaTiO₃) thick films. These films were prepared in two layers geometry using the screen printing technique on Al₂O₃ substrates. Mechanical alloying has been used successfully to produce nanocrystalline powders of hydroxyapatite (HA) used in the films. We also look for the effect of the grain size of the BTO and HA on the final properties of the film. The samples were studied using X-ray diffraction, scanning electron microscopy (SEM), Raman and infrared spectroscopies, dielectric permittivity and losses measurements. The study of the dielectric permittivity and losses was done in the radio-frequency range (100 Hz–10 MHz). The role played by the firing process in the film preparation and the crystallite size of HA and BTO on the dielectric constant and structural properties of the films are discussed.     

Influence of single layer thickness on the performance of undoped and Mg-doped CuCrO<Subscript>2</Subscript> thin films by sol–gel processing

Transparent conductive thin films of copper chromium oxide were processed on borosilicate glass by sol–gel technique. The resistivity of the films was decreased by lowering the single layer thickness of multi-layer stacks deposited by dip-coating, as well as by doping with magnesium. The additional effort of increasing the number of coating cycles from four to fifteen and sintering after each coating resulted in denser films with increased crystallite size. But whereas conductivity was improved by this procedure, the transmittance of the thin films simultaneously dropped by more than 10%. The optimum values obtained for an Mg-doped sample were ρ = 0.38Ω cm at T = 26.8%.