Observation of visible light activated photocatalytic degradation of stearic acid on thin films of tantalum oxynitride synthesized by aerosol assisted chemical vapour deposition.

UV activated photocatalysts deposited using chemical vapour deposition have found commercial success as self-cleaning coatings. However, only limited work has been conducted on the use of the more recently discovered visible light activated photocatalysis for this application. Tantalum oxynitride is an established visible light photocatalyst, and in this paper we have investigated the ability of thin films of tantalum oxynitride to photocatalytically degrade a model organic pollutant, stearic acid, and therefore assess the coatings potential for self-cleaning applications. Thin films of tantalum oxide were formed using aerosol assisted chemical vapour deposition (AACVD) of tantalum ethoxide, and then converted into tantalum oxynitride through ammonolysis at temperatures between 550 °C and 750 °C. Investigation of the films using XRD, UV-vis spectroscopy and XAFS identify that amorphous tantalum oxynitride is formed during the ammonolysis, with complete conversion to TaON under conditions of 700 °C for 24 hours. The self-cleaning ability of this film was assessed using stearic acid as the model pollutant, with a degradation rate of 2.5(2) × 1013 molecules per min per cm2 when exposed to a 5-sun solar simulator, equipped with a UV cut-off filter. We therefore conclude that tantalum oxynitride thin films are able to act as self-cleaning coatings through visible light photocatalysis and that films of tantalum oxynitride can be synthesized using a scalable chemical vapour deposition route.

Phosphinecarboxamide as an unexpected phosphorus precursor in the chemical vapour deposition of zinc phosphide thin films.

This paper demonstrates the use of phosphinecarboxamide as a facile phosphorus precursor, which can be used alongside zinc acetate for the chemical vapour deposition (CVD) of adherent and crystalline zinc phosphide films. Thin films of Zn3P2 have a number of potential applications and phosphinecarboxamide is a safer and more efficient precursor than the highly toxic, corrosive and flammable phosphine used in previous CVD syntheses.

Combining single source chemical vapour deposition precursors to explore the phase space of titanium oxynitride thin films.

In this paper we report on a novel chemical vapour deposition approach to the formation and control of composition of mixed anion materials, as applied to titanium oxynitride thin films. The method used is the aerosol assisted chemical vapour deposition (AACVD) of a mixture of single source precursors. To explore the titanium-oxygen-nitrogen system the single source precursors selected were tetrakis(dimethylamido) titanium and titanium tetraisopropoxide which individually are precursors to thin films of titanium nitride and titanium dioxide respectively. However, by combining these precursors in specific ratios in a series of AACVD reactions at 400 °C, we are able to deposit thin films of titanium oxynitride with three different structure types and a wide range of compositions. Using this precursor system we can observe films of nitrogen doped anatase, with 25% anion doping of nitrogen; a new composition of pseudobrookite titanium oxynitride with a composition of Ti3O3.5N1.5, identified as being a UV photocatalyst; and rock-salt titanium oxynitride in the range TiO0.41N0.59 to TiO0.05N0.95. The films were characterised using GIXRD, WDX and UV-vis spectroscopy, and in the case of the pseudobrookite films, assessed for photocatalytic activity. This work shows that a so-called dual single-source CVD approach is an effective method for the deposition of ternary mixed anion ceramic films through simple control of the ratio of the precursors, while keeping all other experimental parameters constant.

Order of magnitude increase in photocatalytic rate for hierarchically porous anatase thin films synthesized from zinc titanate coatings.

In this paper we report on the use of aerosol assisted chemical vapour deposition (AACVD) to form thin films of the zinc titanate phases using zinc acetate and titanium isopropoxide as precursors in methanol solution. Analysis by XRD and XPS found that through variation in experimental conditions we have been able to synthesize films of zinc titanate with composition of Zn2TiO4 or Zn0.3Ti2.7O4.94, which adopt the spinel and pseudobrookite structure respectively. In addition, we have also formed hybrid films of Zn2TiO4 with either ZnTiO3 or ZnO. Using a technique previously reported with powders, the mixed ZnO and Zn2TiO4 films were treated with acid to produce porous Zn2TiO4 which, through reduction and vapour leaching of zinc, were converted to hierarchically porous thin films of anatase TiO2. This conversion was monitored by XRD. Analysis of photocatalytic activity of the hierarchically porous titania, using dye and stearic acid degradation tests, found a factor of 12 to 14 increase in rates of photocatalysis over conventional TiO2 thin films. Finally we are able to report a maximum formal quantum efficiency for stearic acid degradation of 1.76 × 10-3 molecules per photon.

Synthesis and materials chemistry of bismuth tris-(di-i-propylcarbamate): deposition of photoactive Bi2O3 thin films.

The bismuth carbamate Bi(O2CNPr(i)2)3, a tetramer in the solid-state, has been synthesized and used to deposit mixtures of bismuth oxides by aerosol-assisted chemical vapor deposition (AACVD). The nature of the deposited oxide is a function of both temperature and run-time. Initially, δ-Bi2O3 is deposited, over which grows a thick layer of ß-Bi2O3 nanowires, the latter having an increasing degree of preferred orientation at higher deposition temperatures. The photocatalytic activity of a thin film of δ-Bi2O3 for the degradation of methylene blue dye was found to be similar to that of a commercial TiO2 film on glass, while the film overcoated with ß-Bi2O3 nanowires was less active. Exposure of Bi(O2CNPr(i)2)3 to controlled amounts of moist air affords the novel oxo-cluster Bi8(O)6(O2CNPr(i)2)12, whose structure has also been determined.

New organo- and amidozinc derivatives of primary amines.

Five new zinc derivatives of primary amines [R'ZnN(H)R]2 [R = SiPh3, R' = Me (1), N(SiMe3)2 (4); R = Si(NMe2)3, R' = Me (2), Et (3), N(SiMe3)2 (5)] have been synthesised by reaction of R'2Zn and H2NR. All five species are dimers in which the N-H groups are disposed in a trans manner about a central Zn2N2 ring. In 1 and 4 the coordination at zinc is trigonal planar, while in 2, 3, 5 the zinc is in a distorted tetrahedral environment due to additional Me2N: → Zn coordination from one SiNMe2 group. 5 was found to be generally resistant to NH deprotonation by bases such as MN(SiMe3)2 (M = Li, K) or Zn[N(SiMe3)2]2, but reacts with Sn[N(SiMe3)2]2 to give the tin-free, tetrameric mixed zinc-imido/amido species, [{(Me3Si)2N}{(Me2N)3SiN(H)}{(Me2N)3SiN}Zn2]2 (6) which can be viewed as part of a hexameric Zn6N6 drum which has lost a Zn2N2 ring.

Cobalt(III) diazabutadiene precursors for metal deposition: nanoparticle and thin film growth.

We report the synthesis and characterization of a family of cobalt(III) metal precursors, based around cyclopentadienyl and diazabutadiene ligands. The molecular structure of the complexes cyclopentadienyl-Cobalt(III)(N,N'-dicyclohexyl-diazabutadiene) (2c) and cyclopentadienyl-Cobalt(III)(N,N'-dimesityl-diazabutadiene) (2d) are described, as determined by single crystal X-ray diffraction analysis. Thermogravimetric analysis of the complexes highlighted the isopropyl derivative CpCo((i)Pr2-dab) (2a) as a possible cobalt metal chemical vapor deposition (CVD) precursor. Atmospheric pressure CVD (AP-CVD) was employed using precursor 2a to synthesize thin films of metallic cobalt on silicon substrates under an atmosphere of hydrogen (H2). Analysis of the thin films deposited at substrate temperatures of 250 °C, 275 °C, 300 °C, 325 °C, and 350 °C, respectively, by scanning electron microscopy (SEM) and atomic force microscopy (AFM) reveal temperature dependent growth features: films grown at 325 and 350 °C are continuous and pinhole free, whereas those films grown at substrate temperatures of 250 °C, 275 °C, and 300 °C consist of crystalline nanoparticles. Powder X-ray diffraction (PXRD) and X-ray photoelectron spectroscopy (XPS) all show the films to be high purity metallic cobalt. Raman spectroscopy has also been used to prove the absence of cobalt silicides at the substrate/thin film interface.

Structural tungsten-imido chemistry: the gas-phase structure of W(NBut)2(NHBut)2 and the solid-state structures of novel heterobimetallic W/N/M (M = Rh, Pd, Zn) species.

The gas-phase (electron diffraction) and solid-state (X-ray) structures of W(NBut)2(NHBut)2 (1) have been determined. In the gas phase, 1 adopts both C1 and C2 conformations in a 69:31 ratio. The solid-state structure is disordered over two equal sites, both showing approximate C2 conformation as in the gas phase; the imido and amido centers are, however, clearly distinguished. Compound 1 has been used to synthesize novel heterobimetallic derivatives W(NBut)4[Rh(COD)]2 (3) and W(NBut)4[Pd(eta3-C3H5)]2 (4) via the dilithiated intermediate Li2[W(NBut)4] (2). In both cases, the [W(NBut)4] moiety bridges the two organometallic fragments. Reaction of 1 with Me2Zn has produced [Me(tBuN)W(mu-NBut)2ZnMe(NH2But)] (5). The structures of 3, 4, and 5 have been determined. Thermal decomposition of 4 under an autogenerated pressure at 700 degrees C has formed the hitherto uncharacterized bimetallic alloy WPd2.