Gerry Triani

Controlled pore structure modification of diatoms by atomic layer deposition of TiO2

Diatoms produce diverse three-dimensional, regular silica structures with nanometer to micrometer dimensions and hold considerable promise for biological or biomimetic fabrication of nanostructured materials and devices. The unique hierarchical porous structure of diatom frustules is in particular attractive for membrane applications in microfluidic systems. In this paper, a procedure for pore size modifications of two centric diatom species, Coscinodiscus sp. and Thalassiosira eccentrica (T. eccentrica) using the atomic layer deposition (ALD) of ultrathin films of titanium oxide (TiO2) is described. TiO2 is deposited by sequential exposures to titanium chloride (TiCl4) and water. The modified diatom membranes were characterized using scanning electron microscopy (SEM), atomic force microscopy (AFM), energy dispersive X-ray analysis (EDAX), and secondary ion mass spectrometry (SIMS). These techniques confirmed the controlled reduction of pore sizes while preserving the shape of the diatom membrane pores. Pore diameters of diatom membranes can be further tailored for specific applications by varying the number of cycles and by changing their surface functionality.

Transmission electron microscopy studies of atomic layer deposition TiO2 films grown on silicon

Transmission electron microscopy techniques have been used to characterise atomic layer deposition TiO films grown on 2 silicon substrates after RCA and HF treatment. The influence of deposition temperature (250–350 8C) and substrate type on the film microstructure have been determined. The major influence of substrate type is to control nucleation of crystallisation. HF treated silicon, which was devoid of the native oxide layer, promoted a crystalline, island growth mode. The nucleation of crystalline particles at the onset of deposition resulted in films with very fine grain sizes (f20 nm). The RCA treated silicon, which was coated with amorphous native oxide, caused the growth of an initially amorphous TiO film, which crystallised once 2 a critical film thickness had been exceeded. The major influence of temperature on the films grown on RCA treated silicon was to control nucleation of crystallisation within the amorphous layers, resulting in grain size refinement at higher deposition temperatures. Under the processing conditions used, other than the transient amorphous films formed on RCA treated silicon, anatase was the only phase formed. No evidence for preferred orientation was found. 2003 Elsevier Science B.V. All rights reserved.

Determining the orientation and molecular packing of organic dyes on a TiO2 surface using X-ray reflectometry.

The determination of the orientation and molecular density for several porphyrin dyes adsorbed on planar TiO(2) surfaces using X-ray reflectometry (XRR) is reported. Adsorption of nanoscale water layers occurred rapidly upon exposure of freshly prepared TiO(2) surfaces to ambient conditions; however, this was successfully eliminated, resulting in clearly discernible adsorbed dye layers for sensitized surfaces. Adsorbed dye orientations, determined from computations constrained by the measured dye layer thickness, were calculated to have a binding tilt angle of 35°-40°. Combining the XXR data with the orientation models indicates that the porphyrins form densely packed surfaces with an intermolecular spacing of 3-4 Å, consistent with π-π stacking interactions. Changes in the molecular size of probe dyes were reflected in corresponding changes in the measured dye layer thickness, confirming the ability of this technique to resolve small variations in dye layer thickness and consequently adsorption orientation. Application of these results to understanding the behavior of dye-sensitized devices is discussed.

CO2 Triggering and Controlling Orthogonally Multiresponsive Photochromic Systems

We report a new generic method of reversibly controlling the photochromism of spiropyrans. It was found that the photochromic effect of spiropyrans can be reversibly switched on and off by addition and removal of carbon dioxide (CO(2)) to spiropyran in alcohol solutions containing an amidine (i.e., DBU) that acts as a CO(2) sensitizer. Spiropyrans are not photochromic in the presence of DBU but photochromic when CO(2) is subsequently added to the solution. The CO(2) is readily removed by inert gas bubbling, thus allowing facile activation and deactivation of the photochromic effect. Carbon dioxide, without the presence of the sensitizing amidine, had no effect on photochromism of the spiropyrans. Other photochromic dyes classes such as spirooxazines and chromenes are not affected by this CO(2)/DBU stimulus. As a result, orthogonal activation of mixtures of spirooxazines and spiropyrans was achieved to provide four color states (clear, yellow, green, and blue) by varying the combinations of the stimuli of UV, visible light, CO(2), and CO(2) depleted. This finding now permits the many applications using spiropyrans to be CO(2) responsive.

Atomic layer deposition of TiO2 and Al2O3 thin films and nanolaminates

We have been developing our capability with atomic layer deposition (ALD), to understand the influence of deposition parameters on the nature of TiO2 and Al2O3 films (high and low refractive index respectively), and multilayer stacks thereof (nanolaminates). These stacks have potential applications as anti-reflection coatings and optical filters. This paper will explore the evolution of structure in our films as a function of deposition parameters including temperature and substrate surface chemistry. A broad range of techniques have been applied to the study of these films, including cross-sectional transmission electron microscopy, spectroscopic ellipsometry and secondary-ion mass spectrometry. These have enabled a wealth of microstructural and compositional information on the films to be acquired, such as accurate film thickness, composition, crystallization sequence and orientation with respect to the substrate. The ALD method is shown to produce single-layer films and multilayer stacks with exceptional uniformity and flatness, and in the case of stacks, chemically abrupt interfaces. We are currently extending this technology to the coating of polymeric substrates.

Single and mixed phase TiO2 powders prepared by excess hydrolysis of titanium alkoxide

Abstract To investigate the excess hydrolysis of titanium alkoxides, TiO2 powders were fabricated from titanium tetraisopropoxide using 6∶1 and 100∶1 H2O/Ti (r) ratios. The powders were dried and fired at a range of temperatures (⩽800°C). Hydroxylation and organic content in powders were characterised using attenuated total reflectance Fourier transform infrared spectroscopy (FTIR), laser Raman microspectroscopy and elemental microanalysis; surface area and pore size distribution were evaluated using N2 gas adsorption; phase composition was analysed using X-ray diffraction (XRD) and laser Raman microspectroscopy; and crystallite size was evaluated by XRD, TEM and SEM. Results showed near complete hydrolysis in a predominantly aqueous medium (r = 100), resulting in precipitated crystalline powders exhibiting brookite and anatase, which begin to transform to rutile below 500°C. The powders precipitated in a predominantly organic medium (r = 6) underwent partial hydrolysis, were highly porous and exhibited an amorphous structure, with the crystallisation of anatase occurring at ∼300°C and the transformation to rutile beginning at 500–600°C.

Nanostructured TiO2 membranes by atomic layer deposition

Conformal TiO2 films have been deposited on track-etched polycarbonate membranes by means of atomic layer deposition. Membranes with pore aspect ratios of 25 ∶ 1 and 50 ∶ 1 were selected for initial study. A suite of complementary characterisation techniques was used to probe the nanostructure, stoichiometry and uniformity of the TiO2 coatings. These established that both the surfaces and pores of the membranes were completely covered with an amorphous film. Further, the stoichiometry of the films was close to that of TiO2 though they were found to contain ∼6 atom% chlorine. While the internal walls of the membrane pores were covered with film over their full length, the coating thickness decreased in the direction of gas flow. This was attributed to a variation in reactant concentrations along the pores due to the process conditions. Gas conductance measurements were performed on several coated membranes. These showed that membrane conductance could be controlled by varying the coating thickness.

Atomic Layer Deposition of TiO2 / Al2O3 Films For Optical Applications

Atomic layer deposition (ALD) is an important technology for depositing functional coatings on accessible, reactive surfaces with precise control of thickness and nanostructure. Unlike conventional chemical vapour deposition, where growth rate is dependent on reactant flux, ALD employs sequential surface chemical reactions to saturate a surface with a (sub-) monolayer of reactive compounds such as metal alkoxides or covalent halides, followed by reaction with a second compound such as water to deposit coatings layer-by-layer. A judicious choice of reactants and processing conditions ensures that the reactions are self-limiting, resulting in controlled film growth with excellent conformality to the substrate. This paper investigates the deposition and characterisation of multi-layer TiO2 /Al2O3 films on a range of substrates, including silicon <100>, soda glass and polycarbonate, using titanium tetrachloride/water and trimethylaluminium/water as precursor couples. Structure-property correlations were established using a suite of analytical tools, including transmission electron microscopy (TEM), secondary ion mass spectrometry (SIMS), X-ray reflectometry (XRR) and spectroscopic ellipsometry (SE). The evolution of nanostructure and composition of multi-layer high/low refractive index stacks are discussed as a function of deposition parameters.

Synthesis and characterisation of nanocomposite materials prepared by dispersion of functional TiO2 nanoparticles in PMMA matrix

Composite powders and thin films composed of poly(methyl methacrylate) (PMMA) and functionalised titania nanoparticles are successfully prepared by in situ bulk co-polymerisation using benzoyl peroxide (BPO) as the initiator. The functionalised titania nanoparticles are synthesised by an arrested hydrolysis of Ti(OiPr)4 with either undecylenic (UA) or undecenylphosphonic (UPA) acids used as the organic templates with the long hydrocarbon chains and functional (terminal double bond) groups. Surface-modified TiO2 nanoparticles could be easily dispersed in organic solvent due to the long hydrocarbon chain surrounding the titanium core, and engaged as a co-monomer in polymerisation with the MMA due to the presence of a terminal double bond. TEM and small angle X-ray scattering (SAXS) data presented support the homogeneous and consistent distribution of inorganic phase within the PMMA matrix, with the larger titania nanoparticles detected when the UPA was employed to modify a TiO2 nanoparticle. This is attributed to the UPA greater binding affinity towards the TiO2 surfaces and therefore particles aggregation to some extent.

Novel Chemical Synthesis and Characterization of CeTi2O6 Brannerite

Cerium titanate CeTi2O6 was prepared by a new soft chemistry route in aqueous solution. A suite of characterization techniques, including X-ray diffraction, thermal analysis, vibrational spectroscopy, and scanning and transmission electron spectroscopy, were employed to investigate the brannerite structure formation and its bulk properties. The synthesized powder formed the brannerite crystal structure upon calcination at temperatures as low as 800 °C. Samples sintered at 1350 °C possess a high level of crystallinity. X-ray absorption near-edge structure results indicate the presence of six-coordinated Ce(4+) in the brannerite samples.