Passivation of pigment-grade TiO(2) particles by nanothick atomic layer deposited SiO(2) films

Pigment-grade TiO(2) particles were passivated using nanothick insulating films fabricated by atomic layer deposition (ALD). Conformal SiO(2) and Al(2)O(3) layers were coated onto anatase and rutile powders in a fluidized bed reactor. SiO(2) films were deposited using tris-dimethylaminosilane (TDMAS) and H(2)O(2) at 500?°C. Trimethylaluminum and water were used as precursors for Al(2)O(3) ALD at 177?°C. The photocatalytic activity of anatase pigment-grade TiO(2) was decreased by 98% after the deposition of 2?nm SiO(2) films. H(2)SO(4) digest tests were performed to exhibit the pinhole-free nature of the coatings and the TiO(2) digest rate was 40 times faster for uncoated TiO(2) than SiO(2) coated over a 24?h period. Mass spectrometry was used to monitor reaction progress and allowed for dosing time optimization. These results demonstrate that the TDMAS-H(2)O(2) chemistry can deposit high quality, fully dense SiO(2) films on high radius of curvature substrates. Particle ALD is a viable passivation method for pigment-grade TiO(2) particles.     

Growth of TiO2 with thermal and plasma enhanced atomic layer deposition

We show a comparative study of the TiO2 ALD with TTIP and either O2 or O2-plasma on Si/SiO2 substrates. In particular we compare the surface morphology and crystalline phase by means of Atomic Force Microscopy (AFM), X-ray Photoelectron Spectroscopy (XPS) and X-ray Absorption Spectroscopy (XAS) for different O2-plasma procedures upon changing the time between cycles and the N2-purging pressure. The AFM images show that already these parameters may induce structural changes in the TiO2 films grown by ALD, with the formation of crystallites with average lateral width varying between 15 and 80 nm. By means of XAS we also found that the crystallites have mixed anatase and rutile crystalline phases and that smaller crystallites have a greater rutile component than the larger ones.     

Fabrication of TiO2 nanotubes by atomic layer deposition and their photocatalytic and photoelectrochemical applications

The formation of TiO(2) nanotubes was conducted by atomic layer deposition (ALD) with tris-(8-hydroxyquinoline) gallium (GaQ(3)) nanowires as a template at different substrate temperatures, 50, 100, and 200?°C. TiO(2) nanotubes were formed only at 50 and 100?°C. Although a higher growth rate at 50?°C was observed, nanotubes with better uniformity, conformality, and less residual chloride were obtained at 100?°C because of a different formation mechanism. A photocatalysis test of TiO(2) nanotubes prepared by different cycle numbers at 100?°C was conducted. It showed that TiO(2) nanotubes prepared by 400 cycles of ALD and treated at 700?°C for 1 h to form anatase phase had the best photocatalytic performance. Compared with P-25, the nanotubes showed higher photocatalytic degradation of rhodamine B and water splitting efficiency.     

Laser damage properties of TiO2/Al2O3 thin films grown by atomic layer deposition

Research on thin film deposited by atomic layer deposition (ALD) for laser damage resistance is rare. In this paper, it has been used to deposit TiO(2)/Al(2)O(3) films at 110 °C and 280 °C on fused silica and BK7 substrates. Microstructure of the thin films was investigated by x-ray diffraction. The laser-induced damage threshold (LIDT) of samples was measured by a damage test system. Damage morphology was studied under a Nomarski differential interference contrast microscope and further checked under an atomic force microscope. Multilayers deposited at different temperatures were compared. The results show that the films deposited by ALD had better uniformity and transmission; in this paper, the uniformity is better than 99% over 100 mm Φ samples, and the transmission is more than 99.8% at 1064 nm. Deposition temperature affects the deposition rate and the thin film microstructure and further influences the LIDT of the thin films. As to the TiO(2)/Al(2)O(3) films, the LIDTs were 6.73±0.47 J/cm(2) and 6.5±0.46 J/cm(2) at 110 °C on fused silica and BK7 substrates, respectively. The LIDTs at 11 °C are notably better than 280 °C.     

TiCp*(OMe)3 versus Ti(OMe)4 in atomic layer deposition of TiO2 with water--ab initio modelling of atomic layer deposition surface reactions

It is a common finding that titanocene-derived precursors do not yield TiO2 films in ALD with water. For instance, ALD with Ti(OMe)4 and water gives 0.5 A/cycle, while TiCp*(OMe)3 does not show any growth (Me=CH3, Cp* = C5(CH3)5). This is apparently in contradiction with the computed reactivity of the ligands: the energetics of hydrolysis of the gas-phase precursor indicate that TiCp*(OMe)3 is more reactive to ligand elimination than Ti(OMe)4. However such a model of precursor reactivity neglects surface reactions such as adsorption, diffusion and desorption, all of which can have an important effect on ALD growth rate. A more accurate model of the surface reaction is needed to find the reason for the different behaviours of Ti(OMe)4 and TiCp*(OMe)3 in the ALD process. The more realistic surface model is a TiO2 slab that is periodic in three dimensions. These calculations reveal that TiCp*(OMe)3 does not chemisorb in the usual way because of extreme crowding of the Ti centre by Cp* and that this prevents ALD growth.     

Quantum confinement in amorphous TiO(2) films studied via atomic layer deposition

Despite the significant recent increase in quantum-based optoelectronics device research, few deposition techniques can reliably create the required functional nanoscale systems. Atomic layer deposition (ALD) was used here to study the quantum effects attainable through the use of this ?ngstr?m-level controlled growth process. Size-dependent quantum confinement has been demonstrated using TiO(2) layers of nanoscale thickness applied to the surfaces of silicon wafers. TiO(2) films were deposited at 100?°C using TiCl(4) and H(2)O(2) in a viscous flow ALD reactor, at a rate of 0.61??/cycle. The low-temperature process was utilized to guarantee the amorphous deposition of TiO(2) layers and post-deposition thermal annealing was employed to promote crystallite-size modification. Hydrogen peroxide significantly reduced the residual chlorine that remained from a typical TiCl(4)-H(2)O ALD process at this temperature, down to 1.6%. Spectroscopic ellipsometry was used to quantify the optical properties both below and above the bandgap energy. A central composite design was employed to map the surface response of the film thickness-dependent bandgap shift for the as-deposited case and up to a thermal annealing temperature of 550?°C. The Brus model was used to develop a correlation between the amorphous TiO(2) film thickness and the quantum length to promote equivalent bandgap shifts.     

Al2O3 and TiO2 atomic layer deposition on copper for water corrosion resistance

Al(2)O(3) and TiO(2) atomic layer deposition (ALD) were employed to develop an ultrathin barrier film on copper to prevent water corrosion. The strategy was to utilize Al(2)O(3) ALD as a pinhole-free barrier and to protect the Al(2)O(3) ALD using TiO(2) ALD. An initial set of experiments was performed at 177 °C to establish that Al(2)O(3) ALD could nucleate on copper and produce a high-quality Al(2)O(3) film. In situ quartz crystal microbalance (QCM) measurements verified that Al(2)O(3) ALD nucleated and grew efficiently on copper-plated quartz crystals at 177 °C using trimethylaluminum (TMA) and water as the reactants. An electroplating technique also established that the Al(2)O(3) ALD films had a low defect density. A second set of experiments was performed for ALD at 120 °C to study the ability of ALD films to prevent copper corrosion. These experiments revealed that an Al(2)O(3) ALD film alone was insufficient to prevent copper corrosion because of the dissolution of the Al(2)O(3) film in water. Subsequently, TiO(2) ALD was explored on copper at 120 °C using TiCl(4) and water as the reactants. The resulting TiO(2) films also did not prevent the water corrosion of copper. Fortunately, Al(2)O(3) films with a TiO(2) capping layer were much more resilient to dissolution in water and prevented the water corrosion of copper. Optical microscopy images revealed that TiO(2) capping layers as thin as 200 ? on Al(2)O(3) adhesion layers could prevent copper corrosion in water at 90 °C for ~80 days. In contrast, the copper corroded almost immediately in water at 90 °C for Al(2)O(3) and ZnO films by themselves on copper. Ellipsometer measurements revealed that Al(2)O(3) films with a thickness of ~200 ? and ZnO films with a thickness of ~250 ? dissolved in water at 90 °C in ~10 days. In contrast, the ellipsometer measurements confirmed that the TiO(2) capping layers with thicknesses of ~200 ? on the Al(2)O(3) adhesion layers protected the copper for ~80 days in water at 90 °C. The TiO(2) ALD coatings were also hydrophilic and facilitated H(2)O wetting to copper wire mesh substrates.     

Pechini溶胶-凝胶法制备SiO2/TiO2复合微粒

采用超声St(o)ber法制备了单分散性的纳米载体SiO2,再采用Pechini溶胶-凝胶制备法制备出SiO2/TiO2复合微球.通过X射线衍射仪、场发射扫描电子显微镜(FESEM)对粉体的晶型和显微形貌进行测试分析.结果表明:纳米载体SiO2球形颗粒为无定形态,Ti02粉体为形貌多样的块状颗粒,大颗粒粒径大于10μm...     

TiO2 coating on silica particles by deposition of sol-gel-derived nanoparticles

TiO₂ was coated on nonporous transparent silica particles of 3.2 μm diameter by deposition of sol-gel-derived TiO₂ nanoparticles. Effects of water concentration, feed rate of titanium tetraisopropoxide (TTIP) solution and amount of supplied TTIP solution on the amount of TiO₂ coated on the silica particles were examined. Scanning electron microscopy observation confirmed that TiO₂ was coated on the silica particles in the form of ‘nanoparticles’ by using this method. Because of that, even though the TiO₂ surface area decreased due to sintering after calcination at high temperature to change the crystalline phase of TiO₂ to the anatase phase, the final surface area was still much larger than that of the original silica particles. The results also showed that as the water concentration increased, the amount of coated TiO₂ decreased. On the other hand, when the amount of supplied TTIP solution increased, the amount of coated TiO₂ increased. It was also confirmed that the feed rate of TTIP solution had little effect on the amount of coated TiO₂. The photocatalytic activities of the resulting TiO₂-coated silica particles were also evaluated by the photocatalytic decomposition of 2,4-dinitrophenol as a model substance. The results showed that the photocatalytic activity of the particles is not a function of the total surface area, but of the surface area in which anatase phase TiO₂ is exposed to the reaction space. The sedimentation velocity of the TiO₂-coated silica particles becomes about 5 orders of magnitude faster than that of the primary particles of the TiO₂. This indicates that the handling of the TiO₂ was also improved considerably by coating on the silica particles.     

Enhancement of crystallinity and optical properties of bilayer TiO2/ZnO thin films prepared by atomic layer deposition

Bilayer and multilayer thin films are becoming increasingly important in the development of faster, smaller and more efficient electronic and optoelectronic devices. One of the motivations of applying bilayer or multilayer structures is to modify the optical properties of materials. Atomic layer deposition (ALD) is a variant of Chemical Vapour Deposition that can produce uniform and conformal thin films with well controlled nanostructures. In this study, we have demonstrated new findings of the use of ALD fabricated bilayer TiO2/ZnO thin films with enhanced crystallinity and optical properties. TiO2 films have been deposited at 300 degrees C for 1000 (51 nm in thickness) or 3000 (161 nm in thickness) deposition cycles onto glass and Si substrates. ZnO films are subsequently deposited on the TiO2 layers at 280 degrees C for 500 deposition cycles (55 nm). The crystallinity and optical properties of the TiO2/ZnO thin films have been analysed by X-ray diffraction, photoluminescence, UV-Vis spectroscopy, Atomic Force Microscopy and Scanning Electron Microscopy. XRD diffraction pattern confirmed the presence of ZnO with wutrtize crystal structure and TiO2 with anatase structure. It shows that the crystallinity of the TiO2 films has been improved with the deposition of ZnO. The intensity of UV luminescence has increased by almost 30% for TiO2/ZnO bilayer as compared to the single layer TiO2. The possible mechanism for the enhancement of the optical properties of bilayer TiO2/ZnO thin films will be discussed.     

Ion-assisted deposition of TiO2/SiO2 multilayers for mass production

The optical and microstructural properties of filters composed of TiO2 and SiO2 multilayers deposited by different ion-assisted-deposition (IAD) parameters were investigated. The proper IAD coating conditions for mass-produced, environmentally stable, low-scattering, and low-absorption TiO2/SiO2 multilayers were obtained after comparison of these filters.     

Robust, functional nanocrystal solids by infilling with atomic layer deposition

Thin films of colloidal semiconductor nanocrystals (NCs) are inherently metatstable materials prone to oxidative and photothermal degradation driven by their large surface-to-volume ratios and high surface energies. (1) The fabrication of practical electronic devices based on NC solids hinges on preventing oxidation, surface diffusion, ripening, sintering, and other unwanted physicochemical changes that can plague these materials. Here we use low-temperature atomic layer deposition (ALD) to infill conductive PbSe NC solids with metal oxides to produce inorganic nanocomposites in which the NCs are locked in place and protected against oxidative and photothermal damage. Infilling NC field-effect transistors and solar cells with amorphous alumina yields devices that operate with enhanced and stable performance for at least months in air. Furthermore, ALD infilling with ZnO lowers the height of the inter-NC tunnel barrier for electron transport, yielding PbSe NC films with electron mobilities of 1 cm2 V(-1) s(-1). Our ALD technique is a versatile means to fabricate robust NC solids for optoelectronic devices.     

流态化CVD制备TiO2-ZnS复合粒子的研究

为了制备TiO2-ZnS复合粒子,采用流态化化学气相沉积(CVD)法,探讨了其包覆工艺,借助SEM、XRD、EPMA等测试手段研究了复合粒子结构和包覆过程特征.结果表明:TiO2均匀沉积在ZnS超细颗粒原生粒子表面,形成TiO2-ZnS复合粒子;在包覆过程中同时存在成核和成膜包覆.     

Ultrathin oxide films by atomic layer deposition on graphene

In this paper, a method is presented to create and characterize mechanically robust, free-standing, ultrathin, oxide films with controlled, nanometer-scale thickness using atomic layer deposition (ALD) on graphene. Aluminum oxide films were deposited onto suspended graphene membranes using ALD. Subsequent etching of the graphene left pure aluminum oxide films only a few atoms in thickness. A pressurized blister test was used to determine that these ultrathin films have a Young's modulus of 154 ± 13 GPa. This Young's modulus is comparable to much thicker alumina ALD films. This behavior indicates that these ultrathin two-dimensional films have excellent mechanical integrity. The films are also impermeable to standard gases suggesting they are pinhole-free. These continuous ultrathin films are expected to enable new applications in fields such as thin film coatings, membranes, and flexible electronics.     

Photo-stability of TiO2 particles coated with several transition metal oxides and its measurement by rhodamine-B degradation

Titanium dioxide is the best white pigment, but it does not have good photo-stability if it is not properly coated. As a change from the conventional coating with silicon or aluminum oxide, its photo-stability after coating with zirconium, cerium as well as some other transition metal oxides was investigated. The function of the coated film was to capture electrons and holes of the TiO₂ particles produced by the ultraviolet irradiation that otherwise could produce free radicals on the TiO₂ surface. A new more efficient, easier and more accurate method that used rhodamine-B degradation was used to evaluate the photo-stability of the coated TiO₂ particles. TiO₂ particles coated with the oxides of zirconium, cerium, cobalt or nickel had excellent weather durability, even with only a small amount of coating.     

Monocrystalline zinc oxide films grown by atomic layer deposition

In the present work we report on the monocrystalline growth of (00.1) ZnO films on GaN template by the Atomic Layer Deposition technique. The ZnO films were obtained at temperature of 300 °C using dietylzinc (DEZn) as a zinc precursor and deionized water as an oxygen precursor. High resolution X-ray diffraction analysis proves that ZnO layers are monocrystalline with rocking curve FWHM of the 00.2 peak equals to 0.07°. Low temperature photoluminescence shows a sharp and bright excitonic line with FWHM of 13 meV.     

Effect of deposition temperature on the properties of CeO2 films grown by atomic layer deposition

Cerium oxide dielectric thin films have been grown on n-type silicon by atomic layer deposition using a monomeric homoleptic Ce^IV alkoxide precursor with water vapour. Herein we report the dielectric properties of CeO₂ films deposited from tetrakis(1-methoxy-2-methyl-2-propanolate)cerium. The resulting films exhibit permittivities in the range 25-42 at 1 MHz with a strong dependency on the deposition temperature. The microstructural origin of this behaviour has been investigated. The as-deposited films were found to be crystalline and they exhibited the cubic fluorite structure for deposition temperatures in the range 150 °C to 350 °C. Variations in the crystallite sizes are governed by the deposition temperature and have been estimated using a Debye-Scherrer analysis of the X-ray diffraction patterns. The changing crystallite size correlates with changes seen in the triply-degenerate F_2g first-order Raman line half-width at 465 cm^− 1. It is concluded that the frequency dependency of the film dielectric properties is strongly influenced by the crystallite size which in turn is governed by the growth temperature.     

Organic nanowire-templated fabrication of alumina nanotubes by atomic layer deposition

Alumina nanotubes were fabricated by a template method. Tris-(8-hydroxyquinoline) gallium (GaQ3) organic nanowires were used as a soft template for coating with alumina using an atomic layer deposition technique. The deposition was conducted at 25 degrees C by using trimethylaluminum and distilled water as the precursors of Al2O3. Amorphous alumina nanotubes were obtained after removing the GaQ3 by dissolving in toluene or by heat treatment at 350 degrees C. The amorphous nanotubes could be crystallized by heating at 900 degrees C for 1 h in vacuum.