Chemical vapor deposition and characterization of nitrogen doped TiO2 thin films on glass substrates

Photocatalytically active, N-doped TiO2 thin films were prepared by low pressure metalorganic chemical vapor deposition (MOCVD) using titanium tetra-iso-propoxide (TTIP) as a precursor and NH3 as a reactive doping gas. We present the influence of the growth parameters (temperature, reactive gas phase composition) on the microstructural and physico-chemical characteristics of the films, as deduced from X-ray diffraction (XRD), scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), secondary ion mass spectrometry (SIMS) and ultra-violet and visible (UV/Vis) spectroscopy analysis. The N-doping level was controlled by the partial pressure ratio R=[NH3]/[TTIP] at the entrance of the reactor and by the substrate temperature. For R=2200, the N-doped TiO2 layers are transparent and exhibit significant visible light photocatalytic activity (PA) in a narrow growth temperature range (375–400 °C). The optimum N-doping level is approximately 0.8 at.%. However, the PA activity of these N-doped films, under UV light radiation, is lower than that of undoped TiO2 films of comparable thickness

Chemical vapor infiltration of photocatalytically active TiO2 thin films on glass microfibers

Due to the high diffusivity of the chemical species, chemical vapor infiltration (CVI) is a suitable process for the conformal coverage of objects with large dimensions and complex shape geometry. Its large scale capacity and high reproducibility have made the technique favorable for the deposition of non-oxide ceramics. There are few works on other materials and metal-organic compounds are rarely used as molecular precursors. In this study we focus on the deposition of anatase thin films on substrates with large surface area (microfibers) for photocatalytic air treatment systems. Titanium tetra-isopropoxide (TTIP) was used as precursor without additional oxygen source. Using low mole fractions (26–124×10−5) and low deposition temperatures (300–400 °C), a relatively good thickness uniformity was obtained along the reactor axis. Infiltration experiments were achieved in this temperature range and under 1 Torr for high TTIP diffusivity (110–146 cm2 s−1) and low initial Thiele modulus (0.11–0.13) values. Photocatalytic activity of TiO2 coated glass microfiber samples depends on the film morphology, average thickness and infiltration efficiency. It is shown that this later parameter plays a major role due to the increase of active surface area

Effects of LP-MOCVD prepared TiO2 thin films on the in vitro behavior of gingival fibroblasts

We report on the in vitro response of human gingival fibroblasts (HGF-1 cell line) to various thin films of titanium dioxide (TiO2) deposited on titanium (Ti) substrates by low pressure metal-organic chemical vapor deposition (LP-MOCVD). The aim was to study the influence of film structural parameters on the cell behavior comparatively with a native-oxide covered titanium specimen, this objective being topical and interesting for materials applications in implantology. HGF-1 cells were cultured on three LP-MOCVD prepared thin films of TiO2 differentiated by their thickness, roughness, transversal morphology, allotropic composition and wettability, and on a native-oxide covered Ti substrate. Besides traditional tests of cell viability and morphology, the biocompatibility of these materials was evaluated by fibronectin immunostaining, assessment of cell proliferation status and the zymographic evaluation of gelatinolytic activities specific to matrix metalloproteinases secreted by cells grown in contact with studied specimens. The analyzed surfaces proved to influence fibronectin fibril assembly, cell proliferation and capacity to degrade extracellular matrix without considerably affecting cell viability and morphology. The MOCVD of TiO2 proved effective in positively modifying titanium surface for medical applications. Surface properties playing a crucial role for cell behavior were the wettability and, secondarily, the roughness, HGF-1 cells preferring a moderately rough and wettable TiO2 coating

Low Temperature MOCVD-Processed Alumina Coatings

We first present a Review about the preparation of alumina as thin films by the technique of MOCVD at low temperature (550°C and below). Then we present our results about thin films prepared by the low pressure MOCVD technique, using aluminium tri-isopropoxide as a source, and characterized by elemental analysis (EMPA, EDS, ERDA, RBS), FTIR, XRD and TGA. The films were grown in a horizontal, hot-wall reactor, with N2 as a carrier gas either pure or added with water vapour. The deposition temperature was varied in the range 350-550°C. The films are amorphous. Those prepared at 350°C without water added in the gas phase have a formula close to AlOOH. Those deposited above 415°C are made of pure alumina Al2O3. When water is added in the gas phase, the films are pure alumina whatever the deposition temperature

Grafting luminescent metal-organic species into mesoporous MCM-41 silica from europium(III)tetramethylheptanedionate, Eu(thd)3

Mixed systems with Eu(III) β-diketonates as optically active guest species, and mesoporous silicas MCM-41 as a host matrix have been investigated. The grafting of europium(III) onto the inner walls of unmodified MCM-41 has been achieved starting from Eu(thd)3 (thd = 2,2,6,6- tetramethyl-3,5-heptanedionate), using two routes: wet impregnation (WI) at room temperature,and chemical vapour infiltration (CVI) at 185 °C. In received hybrids, denoted Eu(thd)x@MCM- 41, the same maximum yield [Eu]/[Si] = 8.2 at% on average has been achieved with either methods. The molar ratio x = [thd]/[Eu] is 0.6 on average for WI samples, and 1.5 for CVI samples. In the latter, higher contents in thd compensate lower contents in silanols with respect to the former. Rationalizing the possible bonds exchanged at the silica surface leads to a great diversity of possible co-ordination schemes according to the expression Σ[Si(OH)nx (O)xEu(thd)3-x] (where Σ means that surface species are considered). Chromophore neutral ligands phenanthroline (phen) or bipyridine (bipy) have been added to induce efficient Eu3+ luminescence under 270–280 nm excitation, via the antenna effect. For the most favourable case, (phen)yEu(thd)x@MCM-41, the emission intensity at 612 nm under excitation at 270 nm is 2/3 that for the genuine heteroleptic complex Eu(thd)3(phen). Moreover the hybrid material is stable up to 440 °C

Residual Stress Mechanisms in Aluminum Oxide Films Grown by MOCVD

Residual stresses in amorphous aluminium oxide films were investigated with in situ wafer curvature measurements. The films were deposited from aluminium tri-isopropoxide, on sapphire substrates. Large tensile stresses of 1-2 GPa occurred during growth. These values are well above the fracture stress in bulk materials, but they are sustainable in thin film form. Subsequent heat treatment of these films produced additional tensile stress, even at low temperatures prior to crystallization. The mechanisms responsible for all of these stress contributions are discussed. The variety of operative mechanisms at low to moderate temperatures in these amorphous films suggests that different processing routes can be used to engineer significant differences in the final stress state of these materials

Electrochemical Behavior of Chemical Vapor Deposited Protective Aluminum Oxide Coatings on Ti6242 Titanium Alloy

The electrochemical behavior at room temperature in a neutral sodium chloride aqueous solution of four types of metallorganic chemical vapor deposited aluminum oxide coatings on commercial Ti6242 titanium alloy was investigated. Polarization and electrochemical impedance curves revealed that porosity free, amorphous alumina coatings provide a two order of magnitude improvement of the corrosion resistance with regard to the bare alloy. Crystallized alumina as well as amorphous AlO(OH) only slightly improve the corrosion resistance of Ti6242. It was demonstrated that metallorganic chemical vapor deposition processed amorphous alumina is a highly promising solution to the protection of titanium alloys against corrosion in salt environments

Microfibrous TiO2 supported photocatalysts prepared by metal-organic chemical vapor infiltration for indoor air and waste water purification

The photocatalytic degradation of gaseous (toluene) and aqueous (imazapyr, malic acid, orange G) pollutants over TiO2 supported photocatalysts is investigated using a batch reactor. A strong influence of the microstructural characteristics of TiO2 on the decomposition kinetics of the pollutants is found. Well crystallized, porous TiO2-anatase films grown under low pressure at 400–500 8C by MOCVD on glass plates and by MOCVI on glass micro-fibers are the best heterogeneous photocatalysts, showing the highest activity. We demonstrate a good control of these characteristics by choosing the deposition parameters. Achieving conformal coverage (i.e. good infiltration) of glass micro-fibers by the TiO2 thin films has also a strong influence on the photocatalytic activity. A correlation between optimal infiltration, film microstructure and photocatalytic activity is established. Strong similarities between optimal photocatalytic decomposition rate in gas and liquid phase were found with respect to the film microstructure and the photocatalyst mass. The total mineralization of the toluene was prevented because of the deactivation of the photocatalyst surface. However the reactivation of the photocatalyst was achieved by UV irradiation under oxygen stream. This allows a long-term use of the photocatalyst

Protective Alumina Coatings by Low Temperature Metalorganic Chemical Vapour Deposition

Alumina thin films were processed from aluminium tri-iso-propoxide in a horizontal, with N2 as a carrier gas, occasional addition of water in the gas phase, deposition temperature in the range 350-700°C, total pressure 0.67 kPa (2 kPa when water was used). The films do not diffract X-ray when prepared below 700°C. At 700°C, they start to crystallize as γ-alumina. EDS, EPMA, ERDA, RBS, FTIR and TGA revealed that films prepared in the range 350- 415°C, without water in the gas phase, have an overall composition Al2O3-x(OH)2x, with x tending to 0 with increasing temperature. Al2O3 is obtained above 415°C. When water is added in the vapour phase, the film composition is Al2O3, even below 415°C. Coatings deposited in these conditions show promising protection properties

Phase Transformations of Metallorganic Chemical Vapor Deposition Processed Alumina Coatings Investigated by In Situ Deflection

Phase transformations of Al2O3 films, deposited by metallorganic chemical vapor deposition from aluminium tri-isopropoxide on AISI 301 stainless steel, were investigated using an original technique of deflection associated with X-ray diffraction and electron microscopy. The samples were first oxidized at 1123 K in air to obtain a 0.9 m thick Cr2O3 protective oxide film on one side of the samples. Then, 1 m thick amorphous Al2O3 films were deposited on the opposite side at 823 K and 2 kPa. The deflection of such dissymmetrical samples was recorded during anisothermal treatments, consisting in slow heating to 1173 K in Ar atmosphere. The coefficient of thermal expansion of both the Cr2O3 and the amorphous Al2O3 films was determined to be 710−6 K−1 and 14.7 10−6 K−1, respectively. Crystallization kinetics of amorphous to mainly –Al2O3 become significant at temperatures equal or greater than 983 K. Transformation of metastable Al2O3 to –Al2O3 is initiated below 1173 K. It is demonstrated that deflection is a powerful tool for investigating the behavior of thin films deposited on a substrate and especially to reveal transformations occurring in these films during heat-treatments