Review on Sol-Gel Derived Coatings: Process, Techniques and Optical Applications

Sol-gel process is one of the simplest techniques to manufacture thin films. The quality of the prepared films depends on the parameters of the sol-gel process and the used technique for deposition. A great variety of the sol-gel derived films have been prepared for different applications. We present a review on the sol-gel derived coatings. The description of the process is introduced in details. Different sol-gel deposition techniques are mentioned. The optical applications of the sol-gel derived coatings are reviewed.

SYNTHESIS OF MESOPOROUS POLY(STYRENE-co-MALEIC ANHYDRIDE)/SILICA HYBRID MATERIALS VIA A NONSURFACTANT-TEMPLATED SOL-GEL PROCESS

Mesoporous poly(styrene-co-maleic anhydride)/silica hybrid materials have been prepared. The synthesis was achieved by the HCl-catalyzed sol-gel reactions of tetraethyl orthosilicate (TEOS) and styrene-maleic anhydride copolymer in the presence of 3-aminopropyl triethoxysilane (APTES) as a coupling agent and citric acid as a nonsurfactant template or pore-forming agent, followed by ethanol extraction. Characterization results from nitrogen sorption isotherms and powder X-ray diffraction indicate that polymer-modified mesoporous materials with large specific surface areas (e.g. 900 m(2)/g) and pore volumes (e.g. 0.6 cm(3)/g) could be prepared. As the citric acid concentration is increased, the specific surface areas, pore volumes and pore diameters of the hybrid materials increase.

Preparation of layered oxide Li(Co_(1/3)Ni_(1/3)Mn_(1/3))O_2 via the sol-gel process

To obtain homogenous layered oxide Li（Co1/3Ni1/3Mn1/3）O2 as a lithium insertion positive electrode material, the sol-gel process using citric acid as a chelating agent was applied. The material Li（Co1/3Ni1/3Mn1/3）O2 was synthesized at different calcination temperatures. XRD experiment indicated that the layered Li（Co1/3Ni1/3Mn1/3）O2 material could be synthesized at a lower temperature of 800℃, and the oxidation state of Co, Ni, and Mn in the cathode confirmed by XPS were ＋3, ＋2, and ＋4, respectively. SEM observations showed that the synthesized material could form homogenous particle morphology with the particle size of about 200 nm. In spite of different calcination temperatures, the charge-discharge curves of all the samples for the initial cycle were similar, and the cathode synthesized at 900℃ showed a small irreversible capacity loss of 11.24% and a high discharge capacity of 212.2 mAh·g^-1 in the voltage range of 2.9-4.6 V.

Synthesis and Characterization of Cerium-Doped Lutetium Aluminum Garnet Phosphors by Nitrate-citrate Sol-Gel Combustion Process

Nanosized cerium-doped lutetium aluminum garnet （LuAG：Ce） phosphors were prepared by nitrate-citrate solgel combustion process using 1：1 ratio of the citrate：nitrate. The prepared LuAG：Ce phosphors were characterized by XRD, TEM, photoluminescence and radioluminescence spectra excited by UV and X-ray, respectively. The purified crystalline phase of LuAG：Ce was obtained at 900 ℃ by directly crystallizing from amorphous materials. The resultant Lu- AG：Ce phosphors were uniform and had good dispersivity with an average particle size of about 30 urn. Both photoluminescence and radioluminescence were well-known Ce^3＋ emissions located in the range of 470 -600 nm consisting of two emission bands because of the transition from the lowest 5d excited state （2D） to the 4f ground state of Ce^3＋, which matched well with the sensitivity curve of the Si-photodiode. There was a little red shift for the emission components from the UV-excited emission spectrum to the X-ray-excited emission spectrum. The fast scintillation decay component of 26 ns satisfies the requirements of fast scintillators.

Mechanism of Phase Transformation and Formation of Barium Hexafer rite Doped with Rare-Earths in Sol-Gel Process

The phase-transformation in sol-gel preparation of barium hexaferrite and the formation of barium hexaferrite doped with La 3+ were studied by chemical p hase analysis, X-ray diffraction and infrared spectrometry analysis. The expe rimental results show that phase transformation reactions of FeCO 3, Fe 2O 3 and BaFe 2O 4, barium hexaferrite and γ-Fe 2O 3 take place in the heat tr eatment of gel. While the doping lanthanide ion replace barium ion, an equivalen t quantity of Fe 3+ are reduced to Fe 2+ to maintain the charge equili brium.

Methane reforming with CO_2 to syngas over CeO_2-promoted Ni/Al_2O_3-ZrO_2 catalysts prepared via a direct sol-gel process

CeO2-promoted Ni/Al2O3-ZrO2 （Ni/Al2O3-ZrO2-CeO2） catalysts were prepared by a direct sol-gel process with citric acid as gelling agent. The catalysts used for the methane reforming with CO2 was studied by infrared spectroscopy （IR）, thermal gravimetric analysis （TGA）, microscopic analysis, X-ray diffraction （XRD） and temperature-programmed reduction （TPR）. The catalytic performance for CO2 reforming of methane to synthesis gas was investigated in a continuous-flow micro-reactor under atmospheric pressure. TGA, IR, XRD and microscopic analysis show that the catalysts prepared by the direct sol-gel process consist of Ni particles with a nanostructure of around 5 nm and an amorphous-phase composite oxide support. There exists a chemical interaction between metallic Ni particles and supports, which makes metallic Ni well dispersed, highly active and stable. The addition of CeO2 effectively improves the dispersion and the stability of Ni particles of the prepared catalysts, and enhances the adsorption of CO2 on the surface of catalysts. The catalytic tests for methane reforming with CO2 to synthesis gas show that the Ni/Al2O3-ZrO2-CeO2 catalysts show excellent activity and stability compared with the Ni/Al2O3 catalyst. The excellent catalytic activity and stability of the Ni/Al2O3-ZrO2-CeO2 are attributed to the highly, uniformly and stably dispersed small metallic Ni particles, the high reducibility of the Ni oxides and the interaction between metallic Ni particles and the composite oxide supports.

THE PREPARATION OF PEROVSKITE TYPE STRONTIUM TITANATE BY SOL-GEL PROCESS

By using strontium acetate and titanium n--butoxide [Ti(OBun)4] as starting agents, perovskite -- type double oxide SrTiO3 can be obtained by the sol--gel method. By means of infra-red spectra (IR), X--ray diffraction (XRD), differential thermal analysis (DTG), thermal gravimetry (TG) and scanning electron microscopy (SEM), basical factors, affecting the formation .of SrTiO3,have been discussed. IR results show that the acetic acid as a chelating ligand plays an important role in modifying the whole hydrolysis --condensation process. The addition of glycerol leads to obtaining clear and unique gels. The structure of SrTiO3 calcined at 800℃ is cubic.

Microstructure and electrical properties of La_2 O_3-doped ZnO-based varistor thin films by sol-gel process

Microstructure and electrical properties of La2 O3-doped ZnO-Bi2 O3 thin films prepared by sol–gel process have been investigated.X-ray diffraction shows that most diffraction peaks of ZnO are equal,and the crystals of ZnO grow well.Scanning electron microscopy and atomic force microscopy results indicate that the samples have a good structure and lower surface roughness.The nonlinear V–I characteristics of the films show that La2 O3 develops the electrical properties largely and the best doped content is 0.3% lanthanum ion,with the leakage current of 0.25 mA,the threshold field of 150 V/mm and the nonlinear coefficient of 4.0 in detail.

Preparation of Scratch-Resistant Nano-Porous Silica Films Derived by Sol-Gel Process and Their Anti-reflective Properties

Structural strengthening of the nano porous silica films has been reported. The films were prepared with a base/acid two-step catalyzed TEOS-based sol-gel processing and dip-coating, and then baked in the mixed gas of ammonia and water vapor. The silica films were characterized with TEM, AFM, FTIR, spectrophotometer, ellipsometer, and abrasion test, respectively. The experimental results have shown that the films have a nanostructure with a low refractive index and can form an excellent scratch-resistant broadband anti-reflectance. The two-step catalysis noticeably strengthens the films, and the mixed gas treatment further improves mechanical strength of the silica network. Finally the strengthening mechanism has been discussed.

Growth of TiO_2 Nanorods by Sol-gel Template Process

In this work, TiO2 nanorods with uniform diameter of about 100 nm and a length of several micrometers were successfully prepared by the sol-gel template method. Also the influence of molar ratios of precursor on the morphology and structure of TiO2 nanorods has been investigated. The prepared samples were characterized by Fourier transform infrared spectroscopy （FTIR）, X-ray diffraction （XRD） and scanning electron microscopy （SEM）. The XRD results indicated that the TiO2 nanorods were crystallized in the anatase and rutile phases, after annealing to 400-700℃ up to 2 h.

SYNTHESIS AND OPTICAL PROPERTIES OF A NOVEL ORGANIC/INORGANIC HYBRID NONLINEAR OPTICAL POLYMER VIA SOL-GEL PROCESS

A new organic/inorganic hybrid nonlinear optical (NLO) material was developed by the sol-gel process of an alkoxysilane dye with tetraethoxysilane. A NLO moiety based on 4-nitro-4 ' -hydroxy azobenzene was covalently bonded to the triethoxysilane derivative, i.e, gamma -isocyanatopropyl triethoxysilane. The preparation process and properties of the sol-gel derived NLO polymer were studied and characterized by SEM, FTIR,H-1-NMR, UV-Vis, DSC and second harmonic generation (SHG) measurement. The results indicated that the chemical bonding of the chromophores to the inorganic SiO2 networks induces low dipole alignment relaxation and preferable orientational stability. The SHG measurements also showed that the bonded polymer film containing 75 wt% of the akoxysilane dye has a high electro-optic coefficient (r(33)) of 7.1 pm/V at 1.1 mum wavelength, and exhibit good SHG stability, the r(33) values can maintain about 92.7% of its initial value at room temperature for 90 days, and can maintain about 59.3% at 100 degreesC for 300 min.

PREPARATION AND SECOND-ORDER OPTICAL NONLINEARITY OF NOVEL PHENOXYSILICON NETWORKS BY SOL-GEL PROCESS

Four phenoxysilicon networks for nonlinear optical (NLO) applications were designed and prepared by an extended sol-gel process without additional H2O and catalyst. All poled polymer network films possess high second-order nonlinear optical coefficients (d(33)) Of 10(-7)similar to 10(-8) esu. The investigation of NLO temporal stability at room temperature and elevated temperature (120 degreesC) indicated that these films exhibit high d(33) stability because the orientation of the chromophores are locked in the phenoxysilicon organic/inorganic networks.

Preparation of LiTi_2(PO_4)_3 by the Sol-gel Method and Investigation of Its Formation Process

In this study,a novel solgel method has been developed to prepare LiTi2(PO4)3 lithium ion conductor as monophase at relatively low temperature(600).According to the XRD and IR analysis,the asprepared sample remained an amorphous state up to 500.The activation energy was calculated to be 252 kJ/mol according to the modified Kissinger equation.

RHEOLOGICAL MODIFICATION OF EPOXY RESINS WITH NANO SILICA PREPARED BY THE SOL-GEL PROCESS

Nano silica-modified epoxy resins were synthesized by the sol-gel process, The materials have the morphological structure of nano particales dispersed in the epoxy matrix. The dispersed phase formed a physical network in the resin and thus influenced the rheological behavior greatly. However, the nano silica did not show a significant influence on the mechanical properties of the cured resins.

Facile and Controlled Synthesis of Silica Sol Nanospheres Through a Modifi ed Sol-Gel Process

An effective and reproducible preparation of silica sol nanospheres via a modified sol-gel process has been described. Monodisperse and stable silica sol nanospheres with uniformsize were successfully obtained through the optimized synthesis in which the mixture of tetraethyl orthosilicate （TEOS） and ethanol was followed by the addition of water and ammonium hydroxide （NH3） separately, and the size of silica sol spheres was strictly controlled in the range of 25-119 nm with a narrow size distribution by fine adjustment of several reaction parameters. Results showed that in the presence of low concentration of TEOS, spheres size rose first and reached maximum when H2O concentration was up to 66 g/L. However, the diameter of silica sol spheres decreased above 66 g/L of H2O concentration. Furthermore, it was also found that the size and size distribution of silica sol nanospheres were affected by NH3 concentration. As NH3 concentration increased from 15 to 35 g/L, the diameter declined from 83 to 64 nm. Nevertheless, higher NH3 concentration would result in relatively broad size distribution, and gelation occurred when NH3 concentration reached 44 g/L. In addition, the effect of the different feed rates ofNH3 on the size growth of silica sol nanospheres was also discussed.

Characterization of Bi-substituted Dysprosium Iron Garnet Films Prepared by Sol-gel Process

Bi-substituted dysprosium iron garnet films were prepared by sol-gel process, and were annealed for crystallization. The crystallographic structures of garnet films annealed at different temperatures were analyzed by XRD, the film annealed at 650℃ was polycrystalline garnet with no preferred orientation and no impurity crystalline phase. Magnetic and magneto-optical properties were investigated, the film had magnetic anisotropy perpendicular to the film plane, and exhibited strong coercivity of 1100-1600 Oe and high squareness. These films had large figures of merit applicable to magneto-optic storage, with 2 deg. at λ=430 nm and 1.5 deg. at λ=520 nm respectively.

Synthesis of Anatase TiO_2 Nanoparticles by Improved Sol-Gel Process at Low Temperature

The nanocrystalline TiO_2 powder were prepared by improved sol-gel method at low temperature under ambient pressure. The prepared TiO_2 powder was characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM). It is found that the yield of anatase TiO_2 significantly increases with the reduction of pH by increasing the nucleation rate of anatase. There is an optimum amount of water in sol for the formation of anatase by combining two effects on the concentration of Ti(OH)_4 in gels. Increasing in reaction temperature also benefit to the nucleation of anatase of TiO_2.

Electrical transport and thermoelectric properties of Ni-doped perovskite-type YCo_(1-x)Ni_xO_3 (0 ≤ x ≤ 0.07) prepared by sol-gel process

Electrical transport and thermoelectric properties of Ni-doped YCOl-xNixO3 （0 ≤ x ≤0.07）, prepared by using the sol-gel process, are investigated in a temperature range from 100 to 780 K. The results show that with the increase of Ni doping content, the values of DC resistivity of YCo 1-xNixO3 decrease, but carder concentration increases. The temperature dependences of the resistivity for YCOl-xNixO3 are found to follow a relation of lnp o, lIT in a low-temperature range （LTR） （T 〈- 304 K for x = 0; - 230 K 〈 T 〈- 500 K for x = 0.02, 0.05, and 0.07） and high-temperature range （HTR） （T 〉-655 K for all compounds）, respectively. The estimated apparent activation energies for conduction Eal in LRT and Ea2 in HTR are both found to decrease monotonically with doping content increasing. At very low temperatures （T 〈-230 K）, Mott＇s law is observed for YCOl-xNixO3 （x≥ 0.02）, indicating that considerable localized states form in the heavy doping compounds. Although the Seebeck coefficient of the compound decreases after Ni doping, the power factor of YCOl-xNixO3 is enhanced remarkably in a temperature range from 300 to 740 K, i.e., a 6-fold increase is achieved at 500 K for YCo0.98Ni0.0203, indicating that the high-temperature thermoelectric property of YCoO3 can be improved by partial substitution of Ni for Co.

Formation of High-quality Advanced High-k Oxide Layers at Low Temperature by Excimer UV Lamp-assisted Photo-CVD and Sol-gel Processing

We have successfully demonstrated that high quality and high dielectric constant layers can be fabricated by low temperature photo-induced or -assisted processing. Ta_2O_5 and ZrO_2 have been deposited at t<400 ℃ by means of a UV photo-CVD technique and HfO_2 by photo-assisted sol-gel processing with the aid of excimer lamps. The UV annealing of as-grown layers was found to significantly improve their electrical properties. Low leakage current densities on the order of 10 -8 A/cm 2 at 1 MV/cm for deposited ultrathin Ta_2O_5 films and ca.10 -6 A/cm 2 for the photo-CVD ZrO_2 layers and photo-irradiated sol-gel HfO_2 layers have been readily achieved. The improvement in the leakage properties of these layers is attributed to the UV-generated active oxygen species O( 1D) which strongly oxidize any suboxides to form more stoichiometric oxides on removing certain defects, oxygen vacancies and impurities present in the as-prepared layers. The photo-CVD Ta_2O_5 films deposited across 10.16-cm Si wafers exhibit a high thickness uniformity with a variation of less than \{±2.0%\} being obtained for ultrathin ca.10 nm thick films. The lamp technology can in principle be extended to larger area wafers, providing a promising low temperature route to the fabrication of a range of high quality thin films for future ULSI technology.