Molybdenum-doped vanadium dioxide coatings on glass produced by the aqueous sol-gel method

Thin films of vanadium dioxide (VO₂) on glass substrates were produced by the aqueous sol-gel method. Various levels of doping were achieved by adding small quantities of a water-soluble molybdenum compound to the sol. After dip coating, the substrates were reduced by heat treatment in a low-pressure carbon monoxide/carbon dioxide (CO/CO₂) atmosphere. The change in electrical conductivity with temperature, and optical reflectance in the semiconductor and metallic phases were measured and compared to undoped VO₂ films. Doping the VO₂ films with molybdenum lowered the transition temperature of the semiconductor-to-metal phase change; at a doping level of 7 at.% the transition temperature was measured at 24 °C, as indicated by the electrical conductivity. All the films showed a substantial change in reflectance upon heating through the transition. The optical reflectance in the semiconductor state increased slightly with additional dopant, while the reflectance in the metallic state remained constant.     

A scratch-resistant and hydrophobic broadband antireflective coating by sol-gel method

A double-layer broadband antireflective (AR) and scratch-resistant coating with hydrophobic surface is fabricated via sol-gel process using acid and base catalyzed silica as precursor solutions. The coating is composed of a dense and a porous silica films of which the refractive indices are high and low respectively, realizing a step-index gradient structure with glass as the substrate. The AR property of the coating is optimized to maximize the amplification yield of the laser disk amplifiers used in high power laser system. The average transmittance of BK7 glass coated in this way increased to more than 99.5% over the range of 500 to 850 nm. After NH₃-heat treatment at 200 °C, the scratch-resistance of the coating is improved in a large degree. Trimethylchlorosilane is employed to modify the coating surface to improve the optical stability by resisting moisture. These treatments can ensure that this broadband AR coating is durable for its real application.     

Parameters controlling silver nanoparticle growth in sol-gel silica coatings

Silica based sol-gel coatings doped with different silver amounts have been prepared. Apart from silver concentration, other experimental parameters such as thermal densification conditions, presence of other co-dopants and the nature of the substrate have been varied in order to determine their influence on the final microstructure and properties. Characterisation of the materials prepared was carried out by optical spectroscopy (photoluminescence and absorption), secondary ion mass spectroscopy (SIMS) and transmission electron microscopy (TEM). The study was oriented to determine the parameters governing the nucleation and growth of silver nanoparticles. The results showed that formation of silver nanoparticles was promoted when one or more of the following conditions were achieved: silver concentration in the initial sol over 5%, thermal densification under reducing atmosphere and use of pure silica substrate (in general, glass substrates without modifier ions and, therefore, with few non-bridging oxygen positions).     

基于SPM的花生酸LB膜的拉膜工艺及结构表征的研究

通过扫描探针显微镜（SPM）直接观察沉积在基片表面的花生酸LB（Langmuir-Blodgett）薄膜不同范围尺度下的微观结构.研究在经过表面两亲性（亲水性或疏水性）处理的基片上,在相同的制膜条件下,改变其拉膜沉积方式,对花生酸LB膜样品的表面结构、薄膜均匀性和缺陷等的影响.结果显示,花生酸LB膜在不同拉膜沉积方式下,薄膜表面将形成不同的分子自组装形态;改变基片表面的亲水性强弱也直接影响LB膜的表面形貌的均匀性,可能通过选择恰当表面处理和沉积方式来获得平整度更高,缺陷更少的LB膜.     

Design, fabrication and optical characterization of cerium oxide-magnesium fluoride double layer antireflection coatings on monocrystalline silicon substrates

Theoretical and experimental studies of a double layer antireflection coating deposited onto silicon wafers have been carried out. Magnesium oxide and cerium oxide fabricated by physical vapor deposition method have been applied as low- and high-refractive index materials. MgF₂–CeO₂–Si structures exhibited the reflectivity below 3% in the wavelength window from 0.5 μm to 1.2 μm. Theoretical simulations of spectral characteristics of the reflectivity of these coatings have been performed. A good correlation between experimental data and theoretical curves has been observed with the assumption that a thin SiO₂ layer of a thickness of 16 nm is formed onto Si substrates.     

Synthesis and characterization of nanocrystalline CdZnO thin films prepared by sol-gel dip-coating process

Nanocrystalline Cd_xZn_1 − xO thin films with different Cd volume ratios in solution (x = 0, 0.25, 0.50, 0.75 and 1) have been deposited on glass substrate by sol-gel dip-coating method. The as-deposited films were subjected to drying and annealing temperatures of 275 °C and 450 °C in air, respectively. The prepared films were characterized by X-ray diffraction, scanning electron microscopy, X-ray photoelectron spectroscopy, UV-vis spectroscopy and dc-electrical measurements. The results show that the samples are polycrystalline and the crystallinity of the films enhanced with x. The average grain size is in the range of 20-53 nm. The atomic percent of Cd:Zn was found to be 9.50:1.04, 6.20:3.77 and 4.42:6.61 for x = 0.75, 0.50 and 0.25, respectively. It was observed that the transmittance and the band gap decreased as x increased. All the films exhibit n-type electrical conductivity. The resistivity (ρ) and mobility (μ) are in the range of 3.3 × 10² − 3.4 × 10^− 3 Ω cm, and 1.5 − 45 cm² V^− 1 s^− 1 respectively. The electron density lies between 1.26 × 10¹⁶ and 0.2 × 10²⁰ cm^− 3.     

Optical and structural properties of sol-gel prepared MgZnO alloy thin films

Mg_xZn_1−xO (x = 0-0.5) alloy thin films were prepared by a sol-gel dip-coating method. Mg_0.1Zn_0.9O and Mg_0.5Zn_0.5O films prepared were annealed in the range of 400-900 °C to investigate their thermal stability and temperature-dependent optical properties. The Mg_0.1Zn_0.9O films were thermally stable in the investigated annealing temperature range and exhibited the maximum ultraviolet emission at 800 °C. The segregation of MgO occurred in the Mg_0.5Zn_0.5O films, and the near-band-edge ultraviolet emission of this alloy was enhanced with increasing annealing temperature. The Mg saturation content in the sol-gel prepared MgZnO alloys was found to be about 0.23 where the band gap extended to 3.48 eV.     

Langmuir-Blodgett films of gold/silica core/shell nanorods

We report the preparation of Langmuir- and Langmuir-Blodgett films of mesoporous silica coated gold nanorods. The silica coating on the gold nanorods was found to prevent the aggregation of the plasmonic particles trapped at the air/water interface. Due to the small aspect ratio of the gold core and the presence of the silica shell, the orientational alignment of the nanorods in the Langmuir-Blodgett film is hindered. After particle deposition, no plasmon coupling was observed, which enables the design of the resulting film's optical property at the particle level. By using mesoporous silica as the shell material, the accessibility of the metal core's surface is preserved. Organic dye (Rhodamine 6G) was found to be able to penetrate into the mesoporous shell of the gold nanorods, resulting in a red shift of the longitudinal plasmon mode.     

Evaluation of interfacial shear strength and residual stress of sol-gel derived fluoridated hydroxyapatite coatings on Ti6Al4V substrates

Interfacial shear strength is one of the critical properties in bioceramic coatings on metal implants because it directly affects the success of implantation and long-term stability. In this study, shear strain lag method was employed to evaluate the interfacial shear strength of sol-gel derived fluoridated hydroxyapatite (FHA) coatings on Ti6Al4V substrates. The residual stresses were measured using the “wafer curvature method”. The resultant interfacial shear strength increased from pure HA’s ∼393-459 MPa as fluorine was increased to 1.96 at% and further increased to ∼572 MPa as fluorine increased to 3.29 at%. The residual stresses in the coating also decreased from pure HA’s ∼273-190 MPa and further to ∼137 MPa as fluorine composition in the coating increased. The reduction in the residual stress mainly comes from the reduction in the difference in coefficient of thermal expansion between the coating and the titanium alloy substrate.     

Low temperature sol-gel metal oxide and fluoride layer stacks for optical applications

MgF₂ and TiO₂ single layers and layer stacks were produced by a spin-coating sol-gel process. The final temperature treatment was carried out at 100 °C. The layers were deposited onto silicon and fused silica substrates and were analysed by means of atomic force microscopy, X-ray photoelectron spectroscopy, transmission electron microscopy, ellipsometry, and UV-vis transmission spectroscopy. MgF₂ and TiO₂ single layers have morphological and optical properties comparable with physical vapour deposited layers. By using spectroscopic mapping ellipsometry, a good inter- and intra-sample homogeneity was confirmed. Multiple deposition steps result in a linear increase of layer thickness. Various films were deposited with thicknesses between 25 nm and 350 nm.It was shown that the low temperature sol-gel process results in films of optical quality. Anti-reflective and high reflective layer stacks consisting of MgF₂ and TiO₂ were designed and can be produced now by a sol-gel process, whereas the MgF₂ layers in the layer stacks contains also traces of MgF_2-2xO_x.     

Fabrication of novel sol-gel silica coatings reinforced with multi-walled carbon nanotubes

Novel sol-gel silica coatings reinforced with multi-walled carbon nanotubes (MWCNTs) have been prepared using the organic sol-gel route and the dip-coating technique on magnesium alloy substrates. Homogeneous and dense composite coatings with good reinforcement dispersion were fabricated using low temperature and atmospheric pressure fabrication conditions. The presence of nanotubes caused a substantial enhancement of silica coating fracture toughness on coatings deposited on grounded substrates but it was not as effective on polished substrates because of the low adhesion of the coating to the substrate. Bridging phenomena caused by the MWCNTs was observed, indicating that an effective load transfer between the silica matrix and the nanotube reinforcement was also achieved.     

Novel sol-gel derived calcium phosphate coatings on Mg4Y alloy

Calcium phosphates (CaPs) and silicon containing calcium phosphates (Si-CaPs) coatings on a biodegradable magnesium yttrium alloy (Mg4Y) were prepared by a sol-gel technique to improve the bioactivity of the alloy surface. The experimental results show that thick porous coatings comprised of nano-sized calcium phosphate particles can be prepared by heating the as dip coated substrates at 450 °C. The in vitro degradation results show that the coatings do not alter the degradation kinetics of the substrates significantly and the release of magnesium and yttrium ions at initial time points was very similar for both the coated and bare substrates. The cyto-compatibility studies using MC3T3-E1 osteoblasts show that the coated substrates were more bioactive than the uncoated substrates as the cells begin to grow and form a matrix on the coated substrates more easily than on the bare metal. These preliminary results collectively show the potential of use of sol-gel derived calcium phosphate coatings on magnesium based degradable scaffolds to improve their surface bioactivity.     

Langmuir-Blodgett films of Cu(II)-tetrakis (3,3-dimethylbutoxycarbonyl) phthalocyanine: a spectrophotometric and TEM analysis of their structure and morphology

Langmuir-Blodgett (LB) films of copper(II)-tetrakis (3,3-dimethylbutoxycarbonyl) phthalocyanine [Cu(dmbc)Pc] have been prepared from toluene solutions; multilayers (up to 80 layers) were deposited onto hydrophobic quartz substrates. The refractive index n and extinction coefficient κ at normal incidence have been determined from both transmission and reflection measurements carried out in the 400–800 nm spectral range. The optical absorption spectrum as a function of the incident photon energy was also registered in order to determine the optical transition type in Cu(dmbc)Pc LB films by using a band model approach. Linearly polarised light absorbance measurements were performed at room temperature in the same spectral range. The average orientation of the phthalocyanine molecular rings in the LB film, with respect to the normal to the substrate and the dipping direction, has been evaluated. We have found that such orientation differs from that determined for LB films deposited from ethyl acetate solutions.

Structural and morphological analysis were also carried out by transmission electron microscopy techniques. Small ordered domains in a low range order matrix were observed by high resolution images. The structure of the material in the substrate plane has been determined by electron diffraction performed on single ordered domains.     

Wear resistant coatings: Silica sol-gel reinforced with carbon nanotubes

Pin-on-disc wear experiments have been carried out on sol-gel silica coatings reinforced with 0.1 wt.% carbon nanotubes (CNTs) deposited on WE54 magnesium alloy substrates by the dip-coating technique. Sol-gel solutions were fabricated using two different procedures: mechanical mixing (MM) and ultrasonic probe mixing. Dry sliding wear tests have been carried out at load of 1 N, speed of 0.1 m/s and sliding distance of 60 m. Friction coefficients were obtained from the tests and the specific wear rates (k) were calculated. The fabrication procedure of the coating influences its morphology and wear resistance. Friction coefficient was found to vary slightly with the addition of the CNTs. The wear volume of the magnesium substrate coated decreased by 40% and 80%, in terms of k, by using unreinforced and CNT-reinforced MM coatings, respectively. In MM layers reinforced with CNT uniform dispersion of the nanotubes was reached and toughening of the ceramic coating by pull-out and crack bridging mechanisms was observed.     

Hardness recovery of ceramic coated aluminium matrix composites using thermal-shock resistant sol-gel silica coatings

Sol-gel silica coatings increase wear and corrosion resistance of aluminium matrix composites, but a heat treatment stage at temperatures as high as 500 °C is usually required to consolidate the ceramic coating. Under these thermal conditions, sol-gel ceramic coatings tend to crack and the aluminium matrix hardness strongly reduces. Present paper describes how the combination of a certain sol-gel procedure accompanied with quenching treatment in silicone oil allows recovering most of the hardness of the substrate, while keeping undamaged the sol-gel silica coating deposited.     

Preparation and characterization of sol-gel silica based neutral optical density coatings by the addition of graphite particles

Silica based coatings with various thicknesses (600-3000 nm) were prepared from the gellation of aqueous suspensions composed of colloidal silica particles, small graphite particles and inorganic binder materials, the latter were included to improve the coating structure. The graphite particles added in amounts of 0.8-3.6 wt.%, in the dried coating, absorb visible light with the same efficiency, which results in coatings with neutral optical density in this range of the spectrum. The optical density of the coatings can be changed from basically 0, in coatings without graphite, to more than 2 in thick coatings with 3.6 wt.% of graphite. The structural characterization of the coatings was carried out using X-ray diffraction, Raman scattering and atomic force microscopy.     

Structural and optical properties of n-propoxide sol-gel derived ZrO2 thin films

In this work, we present a sol-gel method for the preparation of zirconia films. Using zirconium n-propoxide as the starting precursor, a ZrO₂ sol has been synthesized that remains stable for several months. Thin films were deposited using the dip-coating method. The structural characterization was performed using waveguide Raman spectroscopy. The films present an amorphous phase up to an annealing temperature of 400 °C. Both monoclinic and tetragonal phases were obtained for annealing temperatures higher than 450 °C. The proportions of these two phases were calculated from the Raman spectra and the size of the crystallites was evaluated using the low-wavenumber Raman band. The optical properties were characterized by the m-lines technique (n = 1.96) and UV-visible spectroscopy. The optical losses for a TE₀ mode were measured to be 0.29 ± 0.03 dB cm^− 1 for a sample annealed at 400 °C. To optimize the protocol for thermal annealing, a powder obtained from a dried sol was characterized by Thermal Gravimetric Analysis. Rutherford Back Scattering was employed to determine the chemical composition and the stoichiometry of the zirconia films.     

Waveguiding terbium-doped yttrium aluminum garnet coatings based on the sol-gel process

Multi-layer luminescent Y₃Al₅O₁₂:Tb³⁺ coatings have been prepared by the sol-gel route from alkoxide precursors. Highly transparent and crack-free 700-800 nm thick films were produced by the dip-coating technique from sols stabilized with acetylacetone as a chelating agent. High-temperature X-ray diffraction analysis shows that the films start to crystallize at 850 °C. On the basis of atomic force and scanning electron microscopies, it has been observed to have uniform and smooth surfaces. Waveguiding properties have been demonstrated by m-lines spectroscopy giving refractive index values of transverse electric and magnetic modes very close each other and the same thickness for both modes. These properties have only been observed for amorphous films, crystallization entailing the vanishment of waveguiding properties. Xe-lamp induced emission spectra of Tb³⁺ ions were recorded from amorphous and crystallized dip-coated films respectively annealed at 400 °C and 1000 °C. Spectra reveal the characteristic green emission arising from the Tb^{3+ 5}D₄ manifold for both samples.     

A study towards improving mechanical properties of sol-gel coatings for polycarbonate

Scratch-resistant coatings based on 3-glycidoxypropyltrimethoxysilane and tetraethylorthosilicate with a cross-linking agent and different amounts of colloidal silica are prepared on polycarbonate substrates by sol-gel technique. The failure mode of this type of coating on soft plastic substrate under pencil scratch test is studied. It is found that the pencil scratch failure contains a gouge failure under the static pressure and a film cracking failure under the sliding of the pencil tip. The gouge failure is due to the early plastic deformation in the substrate, while the film cracking is due to the tensile stress in the film induced by the sliding and friction of the pencil tip. Factors influencing the static gouge failure and sliding cracking failure are investigated. It is found that the cross-linking agent and colloidal silica filler increase the intrinsic cross-linking, hardness, elastic modulus and fracture toughness of the coating material, therefore, reduce the film cracking tendency; whereas the increased layer thickness and multi-layer coating improve the pencil scratch resistance significantly via delayed plastic deformation in the substrate. Based on these analyses, we conclude that the main factors towards improved pencil scratch resistance are: layer thickness, elastic modulus, fracture toughness and intrinsic hardness of the coating material. Pencil hardness is increased from grade 2B to 5H by adjusting these parameters.     

Interfacial study of magnesium-containing fluoridated hydroxyapatite coatings

Magnesium-containing fluoridated hydroxyapatite (Mg_xFHA) coatings have been developed to improve the biological performances of fluoridated hydroxyapatite (FHA) coatings. The coatings are deposited on Ti6Al4V substrates via a sol-gel process. The interface between the coating and substrate is characterized by scanning electron microscopy, glow discharge optical emission spectroscopy and X-ray photoelectron spectroscopy for coating thickness, elemental distribution and chemical states. Pull-off test is used to evaluate the adhesion strength. The results show that the interdiffusion of elements happens at the coating/substrate interface. The incorporation of Mg ions into FHA coatings enhances the pull-off adhesion strength between the coating and the substrate, but no significant difference is observed with different Mg concentrations.