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As a very promising thermochromic material, VO2 (M/R) (Monoclinic/Rutile) has not been widely applied in smart windows due to its intrinsic low solar modulation (ΔTsol) and low luminous transmission (Tlum). To address this issue, porous structures have been introduced into the VO2 film. Herein, mesoporous VO2 powders with pore size of about 2–10 nm were synthesized using cotton as template by hydrothermal methods. The pore and crystal size of the synthesized VO2 powders can be reliably controlled by the hydrothermal temperature. The mesoporous VO2 powders were mixed with PVP to prepare the VO2-based nanocomposite films by spin coating. The VO2-based films show a better performance between ΔTsol and Tlum than that appeared in previous reports. Especially, a larger pore size could lead to a higher visible transmittance and a larger crystal size would facilitate the enhancement in the solar modulation. In this sense, the VO2-based film obtained at the hydrothermal temperature of 180 °C exhibits an outstanding thermochromic performance with ΔTsol of 12.9% and Tlum up to 56.0% due to a larger crystal size and pore size. Therefore, this synthetic route shows a potential method for the application of mesoporous VO2 powders for solar control coatings.

A method of quantitative phase analysis using valence band X-ray photoelectron spectra is presented and applied to the analysis of TiO2 anatase-rutile mixtures. The valence band spectra of pure TiO2 polymorphs were measured, and these spectral shapes used to fit valence band spectra from mixed phase samples. Given the surface sensitive nature of the technique, this yields a surface phase fraction. Mixed phase samples were prepared from high and low surface area anatase and rutile powders. In the samples studied here, the surface phase fraction of anatase was found to be linearly correlated with photocatalytic activity of the mixed phase samples, even for samples with very different anatase and rutile surface areas. We apply this method to determine the surface phase fraction of P25 powder. This method may be applied to other systems where a surface phase fraction is an important characteristic.

The limit of solubility of Ga2O3 in the cubic bixbyite In2O3 phase was established by X-ray diffraction and Raman spectroscopy to correspond to replacement of around 6% of In cations by Ga for samples prepared at 1250 °C. Density functional theory calculations suggest that Ga substitution should lead to widening of the bulk bandgap, as expected from the much larger gap of Ga2O3 as compared to In2O3. However both diffuse reflectance spectroscopy and valence band X-ray photoemission reveal an apparent narrowing of the gap with Ga doping. It is tentatively concluded that this anomaly arises from introduction of Ga+ surface lone pair states at the top of the valence band and structure at the top of the valence band in Ga-segregated samples is assigned to these lone pair states. In addition photoemission reveals a broadening of the valence band edge. Core X-ray photoemission spectra and low energy ion scattering spectroscopy both reveal pronounced segregation of Ga to the ceramic surface, which may be linked to both relief of strain in the bulk and the preferential occupation of surface sites by lone pair cations. Surprisingly Ga segregation is not accompanied by the development of chemically shifted structure in Ga 2p core XPS associated with Ga+. However experiments on ion bombarded Ga2O3, where a shoulder at the top edge of the valence band spectra provide a clear signature of Ga+ at the surface, show that the chemical shift between Ga+ and Ga3+ is too small to be resolved in Ga 2p core level spectra. Thus the failure to observe chemically shifted structure associated with Ga+ is not inconsistent with the proposal that band gap narrowing is associated with lone pair states at surfaces and interfaces.

TiO2 thin films prepared by sol–gel synthesis were N-doped by post treating with liquid ammonia and annealing at 500 °C. Characterisation by X-ray diffraction and Raman spectroscopy confirmed that the anatase crystal type was retained and present in all samples. Scanning electron microscopy showed that treatment with liquid ammonia had no significant effect on the film morphology. Functional testing under filtered while light conditions involving water contact angle, and the photo destruction of both Resazurin and Stearic acid showed the ammonia treated samples to be active visible light photocatalysts in contrast to the pure TiO2 and the blank controls. X-ray Photoelectron Spectroscopy studies indicate the presence of interstitial nitrogen (N1s = 400 eV) suggesting that the origin of the enhanced photocatalytic activity is most likely due to oxygen vacancies created by the interstitial nitrogen incorporation. This synthesis method utilises a simple, inexpensive and highly effective post treatment route to N-dope TiO2 and produces visible light photocatalysts with potential applications in self-cleaning and healthcare environments.

Nanocrystalline anatase (TiO2) thin films prepared by a physical vapour deposition method were nitrided by annealing in flowing NH3 at temperatures ranging between 650 °C and 700 °C. It was established that there was a narrow window of temperatures which allowed both incorporation of interstitial nitrogen into the films with retention of the anatase phase without chemical reduction and preservation of the characteristic nanocrystalline morphology. These optimally modified films responded to visible light in photowetting tests and showed the ability to degrade an organic dye under visible light irradiation. © 2011 Elsevier B.V. All rights reserved.

Atmospheric pressure chemical vapour deposition of tin monoselenide and tin diselenide films on glass substrate was achieved by reaction of diethyl selenide with tin tetrachloride at 350–650 °C. X-ray diffraction showed that all the films were crystalline and matched the reported pattern for SnSe and/or SnSe2. Wavelength dispersive analysis by X-rays show a variable Sn:Se ratio from 1:1 to 1:2 depending on conditions. The deposition temperature, flow rates and position on the substrate determined whether mixed SnSe–SnSe2, pure SnSe or pure SnSe2 thin films could be obtained. SnSe films were obtained at 650 °C with a SnCl4 to Et2Se ratio greater than 10. The SnSe films were silver–black in appearance and adhesive. SnSe2 films were obtained at 600–650 °C they had a black appearance and were composed of 10 to 80 μm sized adherent crystals. Films of SnSe only 100 nm thick showed complete absorbtion at 300–1100 nm.

Structural studies by X-ray crystallography have been carried out for a range of diorganoalkoxogallanes incorporating donor-functionalized ligands. The compounds [Et2Ga(μ-OR)]2 (1, R = CH2CH2NMe2; 2, R = CH(CH3)CH2NMe2; 3, C(CH3)2CH2OMe; 4, R = CH(CH2NMe2)2) adopt dimeric structures with a planar Ga2O2 ring, and each gallium atom is coordinated in a distorted trigonal bipyramidal geometry. Low pressure chemical vapor deposition (CVD) of 2 and 4 resulted in the formation of oxygen deficient gallium oxide thin films on glass. However, the reaction of Et3Ga and ROH (R = CH2CH2NMe2, CH(CH3)CH2NMe2, C(CH3)2CH2OMe, CH(CH2NMe2)2) in toluene under aerosol assisted (AA)CVD conditions afforded stoichiometric Ga2O3 thin films on glass. This CVD technique offers a rapid, convenient route to Ga2O3, which involves the in situ formation of diethylalkoxogallanes, of the type [Et2Ga(μ-OR)]2, the structures of which are described in this paper. The gallium oxide films were deposited at 450 °C and analyzed by scanning electron microscopy (SEM), X-ray powder diffraction, wavelength dispersive analysis of X-rays (WDX), X-ray photoelectron spectroscopy (XPS) and Raman spectroscopy.