Monoclinic vanadium(IV) oxide (VO2) has been widely studied for energy-efficient glazing applications because of its thermochromic properties, displaying a large change in transmission of near-IR wavelengths between the hot and cold states. The optimization of the reaction between VCl4 and ethyl acetate via atmospheric-pressure chemical vapor deposition (APCVD) was shown to produce thin films of monoclinic VO2 with excellent thermochromic properties (ΔTsol = 12%). The tailoring of the thermochromic and visible light transmission was shown to be possible by altering the density and morphology of the deposited films. The films were characterized by X-ray diffraction, atomic-force microscopy, scanning electron microscopy, ellipsometry, and UV–vis spectrometry. This article provides useful design rules for the synthesis of high-quality VO2 thin films by APCVD.Topics: Deposition process; Mass transfer; Mass transfer; Optical properties; Phase transition; Pressure; Process control; Spectra; Surface structure;

Graphitic carbon nitrides (GCNs) represent a family of 2D materials composed of carbon and nitrogen with variable amounts of hydrogen, used in a wide variety of applications. We report a method of room temperature thin film deposition which allows ordered GCN layers to be deposited on a very wide variety of substrates, including conductive glass, flexible plastics, nanoparticles and nano-structured surfaces, where they form a highly conformal coating on the nanoscale. Film thicknesses of below 20 nm are achievable. In this way we construct functional nanoscale heterojunctions between TiO2 nanoparticles and GCN, capable of producing H2 photocatalytically under visible light irradiation. The films are hydrogen rich, have a band gap around 1.7 eV, display transmission electron microscopy lattice fringes as well as X-ray diffraction peaks despite being deposited at room temperature, and show characteristic Raman and IR bands. We use cluster etching to reveal the chemical environments of C and N in GCN using X-ray photoelectron spectroscopy. We elucidate the mechanism of this deposition, which operates via sequential surface adsorption and reaction analogous to atomic layer deposition. The mechanism may have implications for current models of carbon nitride formation.

The tolerance factor is a widely used predictor of perovskite stability. The recent interest in hybrid perovskites for use as solar cell absorbers has lead to application of the tolerance factor to these materials as a way to explain and predict structure. Here we critically assess the suitability of the tolerance factor for halide perovskites. We show that the tolerance factor fails to accurately predict the stability of the 32 known inorganic iodide perovskites, and propose an alternative method. We introduce a revised set of ionic radii for cations that is anion dependent, this revision is necessary due to increased covalency in metal–halide bonds for heavier halides compared with the metal-oxide and fluoride bonds used to calculate Shannon radii. We also employ a 2D structural map to account for the size requirements of the halide anions. Together these measures yield a simple system which may assist in the search for new hybrid and inorganic perovskites.

The nature and effects of rhodium and antimony doping in TiO2 have been investigated using X-ray diffraction (XRD), X-ray Photoelectron Spectroscopy (XPS), Extended X-ray Absorption Fine Structure (EXAFS) analysis, X-ray Absorption Near Edge Structure (XANES) analysis and diffuse reflectance spectroscopy. Together these techniques build up a comprehensive picture of the dopant chemistry in this system. A range of Sb/Rh ratios have been analysed, and it is shown that the Fermi level can be tuned within the band gap through control of dopant stoichiometry, offering the possibility of designing Z-scheme components with specific band offsets. Spontaneous spatial segregation of dopants is measured using TiO2 (110) single crystals. This is shown to have a direct impact on the electronic structure in the region of the semiconductor surface, creating band bending that is expected to be critical for photocatalytic activity of these materials.

Novel lead and bismuth dipyrido complexes have been synthesized and characterized by single-crystal X-ray diffraction, which shows their structures to be directed by highly oriented π-stacking of planar fully conjugated organic ligands. Optical band gaps are influenced by the identity of both the organic and inorganic component. Density functional theory calculations show optical excitation leads to exciton separation between inorganic and organic components. Using UV–vis, photoluminescence, and X-ray photoemission spectroscopies, we have determined the materials’ frontier energy levels and show their suitability for photovoltaic device fabrication by use of electron- and hole-transport materials such as TiO2 and spiro-OMeTAD respectively. Such organic/inorganic hybrid materials promise greater electronic tunability than the inflexible methylammonium lead iodide structure through variation of both the metal and organic components.

Methyl-ammonium lead iodide is the archetypal perovskite solar cell material. Phase pure, compositionally uniform methyl-ammonium lead iodide thin films on large glass substrates were deposited using ambient pressure aerosol assisted chemical vapour deposition. This opens up a route to efficient scale up of hybrid perovskite film growth towards industrial deployment.

The tolerance factor is a widely used predictor of perovskite stability. The recent interest in hybrid perovskites for use as solar cell absorbers has lead to application of the tolerance factor to these materials as a way to explain and predict structure. Here we critically assess the suitability of the tolerance factor for halide perovskites. We show that the tolerance factor fails to accurately predict the stability of the 32 known inorganic iodide perovskites, and propose an alternative method. We introduce a revised set of ionic radii for cations that is anion dependent, this revision is necessary due to increased covalency in metal–halide bonds for heavier halides compared with the metal-oxide and fluoride bonds used to calculate Shannon radii. We also employ a 2D structural map to account for the size requirements of the halide anions. Together these measures yield a simple system which may assist in the search for new hybrid and inorganic perovskites.

Methyl-ammonium lead iodide is the archetypal perovskite solar cell material. Phase pure, compositionally uniform methyl-ammonium lead iodide thin films on large glass substrates were deposited using ambient pressure aerosol assisted chemical vapour deposition. This opens up a route to efficient scale up of hybrid perovskite film growth towards industrial deployment.

Highly oriented TiO2 thin films were deposited onto Al2O3(0001), SrTiO3(001), and LaAlO3(001) substrates by spin coating a titanium alkoxide precursor solution followed by annealing. The films were nitrogen doped by two different routes: either by adding tetramethyethylenediamine (TMEDA) to the precursor solution or alternatively by high temperature ammonolysis. Undoped TiO2 films were highly oriented and the phase was dependent on the substrate. N doping by ammonolysis led to transformation of rutile films to anatase, confirmed by XRD and by XPS valence band spectroscopy. Significant differences were observed in the spatial distribution of the nitrogen dopant depending upon which synthesis method was used. These two factors may shed light on the increased photocatalytic efficiencies reported in N doped TiO2.

The nature and effects of rhodium and antimony doping in TiO2 have been investigated using X-ray diffraction (XRD), X-ray Photoelectron Spectroscopy (XPS), Extended X-ray Absorption Fine Structure (EXAFS) analysis, X-ray Absorption Near Edge Structure (XANES) analysis and diffuse reflectance spectroscopy. Together these techniques build up a comprehensive picture of the dopant chemistry in this system. A range of Sb/Rh ratios have been analysed, and it is shown that the Fermi level can be tuned within the band gap through control of dopant stoichiometry, offering the possibility of designing Z-scheme components with specific band offsets. Spontaneous spatial segregation of dopants is measured using TiO2 (110) single crystals. This is shown to have a direct impact on the electronic structure in the region of the semiconductor surface, creating band bending that is expected to be critical for photocatalytic activity of these materials.