Dispelling the Myth of Passivated Codoping in TiO2

Modification of TiO2 to increase its visible light activity and promote higher performance photocatalytic ability has become a key research goal for materials scientists in the past 2 decades. One of the most popular approaches proposed this as “passivated codoping”, whereby an equal number of donor and acceptor dopants are introduced into the lattice, producing a charge neutral system with a reduced band gap. Using the archetypal codoping pairs of [Nb + N]- and [Ta + N]-doped anatase, we demonstrate using hybrid density functional theory that passivated codoping is not achievable in TiO2. Our results indicate that the natural defect chemistry of the host system (in this case n-type anatase TiO2) is dominant, and so concentration parity of dopant types is not achievable under any thermodynamic growth conditions. The implications of passivated codoping for band gap manipulation in general are discussed

Resonant Ta Doping for Enhanced Mobility in Transparent Conducting SnO2

Transparent conducting oxides (TCOs) are ubiquitous in modern consumer electronics. SnO2 is an earth abundant, cheaper alternative to In2O3 as a TCO. However, its performance in terms of mobilities and conductivities lags behind that of In2O3. On the basis of the recent discovery of mobility and conductivity enhancements in In2O3 from resonant dopants, we use a combination of state-of-the-art hybrid density functional theory calculations, high resolution photoelectron spectroscopy, and semiconductor statistics modeling to understand what is the optimal dopant to maximize performance of SnO2-based TCOs. We demonstrate that Ta is the optimal dopant for high performance SnO2, as it is a resonant dopant which is readily incorporated into SnO2 with the Ta 5d states sitting ∼1.4 eV above the conduction band minimum. Experimentally, the band edge electron effective mass of Ta doped SnO2 was shown to be 0.23m0, compared to 0.29m0 seen with conventional Sb doping, explaining its ability to yield higher mobilities and conductivities

Carbon nanotubes in TiO₂ nanofiber photoelectrodes for high-performance perovskite solar cells

1D semiconducting oxides are unique structures that have been widely used for photovoltaic (PV) devices due to their capability to provide a direct pathway for charge transport. In addition, carbon nanotubes (CNTs) have played multifunctional roles in a range of PV cells because of their fascinating properties. Herein, the influence of CNTs on the PV performance of 1D titanium dioxide nanofiber (TiO2 NF) photoelectrode perovskite solar cells (PSCs) is systematically explored. Among the different types of CNTs, single-walled CNTs (SWCNTs) incorporated in the TiO2 NF photoelectrode PSCs show a significant enhancement (≈40%) in the power conversion efficiency (PCE) as compared to control cells. SWCNTs incorporated in TiO2 NFs provide a fast electron transfer within the photoelectrode, resulting in an increase in the short-circuit current (J sc) value. On the basis of our theoretical calculations, the improved open-circuit voltage (V oc) of the cells can be attributed to a shift in energy level of the photoelectrodes after the introduction of SWCNTs. Furthermore, it is found that the incorporation of SWCNTs into TiO2 NFs reduces the hysteresis effect and improves the stability of the PSC devices. In this study, the best performing PSC device constructed with SWCNT structures achieves a PCE of 14.03%

Aerosol-assisted fabrication of tin-doped indium oxide ceramic thin films from nanoparticle suspensions

Sn-doped In2O3 (ITO) thin films were fabricated on float glass substrates from a nanoparticle suspension using a new and inexpensive aerosol-assisted chemical transport (AACT) process. The influence of the solvent type, loading level and film deposition time on the structural, electrical and optical properties of the deposited thin films was investigated. In addition, the effect of post-deposition heat-treatment of ITO films on the film resistivity and transparency was investigated using microwave radiation and compared with more conventional radiant heat-treated films. The SEM images of the films prepared using a 30 min deposition time with 0.20% (wt/vol%) methanolic ITO suspension provided better surface coverage compared to the other deposition times investigated. The optimised ITO films were heat-treated after deposition by either conventional radiant or microwave assisted heating methods in order to improve the inter-particle connections and film adherence. The films heat-treated after deposition by microwave annealing exhibited an average transmittance of >85% in the visible region with a resistivity of 12 Ω cm and a carrier concentration of -3.7 x 1016 cm 3 , which was superior to films that were heat-treated using more conventional thermal processing (despite the shorter processing time for the microwave process). The resistivity of ITO films was further decreased to 6.0 x 10-2 Ω cm with increased carrier concentration of -8.0 x 1018 cm 3 when ethyl cellulose was added to the ITO suspension prior to the AACT deposition. The enhanced conductivity of this film is due to the improved particle-particle and particle-substrate connections as observed by SEM imaging

Dispersion and microwave processing of nano-sized ITO powder for the fabrication of transparent conductive oxides

Aqueous dispersions of tin-doped indium oxide (ITO) nanopowder were prepared and the effect of the addition of PEG 400, Tween 80 and β-alanine as dispersants was investigated using zeta potential and particle size distribution measurements. Both PEG 400 and β-alanine were found to produce stable dispersions that were used to deposit ITO thin films on glass substrates by dip and spin coating methods. The ITO thin films were heat-treated using both conventional and microwave heat treatment in order to improve the inter-particle connections and hence the resistivity and transparency of the films. All the films exhibited an average transmittance of >80% over the visible spectrum after being subjected to the heat treatment process. ITO films prepared with no dispersant showed very high resistivity values for both heating methods, however addition of 2 wt% PEG 400 to the dispersion yielded a reduction in the resistivity values to 1.4×10−1 Ω cm and 3.8×10−2 Ω cm for conventionally and microwave treated films, respectively. The surface morphological studies confirmed that addition of dispersants improved the film uniformity and inter-particle connections of the ITO films considerably

Atmospheric pressure chemical vapour deposition of chromium oxide films

Cr2O3 films have been deposited on glass substrates by atmospheric pressure chemical vapour deposition reaction of chromyl chloride with either water, ethyl acetate, methanol or ethanol. Films were deposited in the temperature range 450 °C - 600 °C. The Cr2O3 films were characterised by glancing angle XRD, SEM and X-ray photoelectron spectroscopy. These analyses showed that singlephase Cr2O3 was obtained at all deposition temperatures

A comprehensive aerosol spray method for the rapid photocatalytic grid area analysis of semiconductor photocatalyst thin films

Indicator inks, previously shown to be capable of rapidly assessing photocatalytic activity via a novel photo-reductive mechanism, were simply applied via an aerosol spray onto commercially available pieces of ActivTM self-cleaning glass. Ink layers could be applied with high evenness of spread, with as little deviation as 5% upon UV-visible spectroscopic assessment of 25 equally distributed positions over a 10cm×10cm glass cut. The inks were comprised of either a resazurin (Rz) or dichloroindophenol (DCIP) redox dye with a glycerol sacrificial electron donor in an aqueous hydroxyethyl cellulose (HEC) polymer media. The photo-reduction reaction under UVA light of a single spot was monitored by UV-vis spectroscopy and digital images attained from a flat-bed scanner in tandem for both inks. The photo-reduction of Rz ink underwent a two-step kinetic process, whereby the blue redox dye was initially reduced to a pink intermediate resorufin (Rf) and subsequently reduced to a bleached form of the dye. In contrast, a simple one-step kinetic process was observed for the reduction of the light blue redox dye DCIP to its bleached intermediates. Changes in red-green-blue colour extracted from digital images of the inks were inversely proportional to the changes seen at corresponding wavelengths via UV-visible absorption spectroscopy and wholly indicative of the reaction kinetics. The photocatalytic activity areas of cuts of ActivTM glass, 10cm×10cm in size, were assessed using both Rz and DCIP indicator inks evenly sprayed over the films; firstly using UVA lamp light to activate the underlying ActivTM film (1.75mWcm−2) and secondly under solar conditions (2.06±0.14mWcm−2). The photo-reduction reactions were monitored solely by flatbed digital scanning. Red-green-blue values of a generated 14×14 grid (196 positions) that covered the entire area of each film image were extracted using a custom-built program entitled RGB Extractor(C). A homogenous degradation over the 196 positions analysed for both Rz (Red colour deviation = 19% UVA, 8% Solar; Green colour deviation = 17% UVA, 12% Solar) and DCIP (Red colour deviation = 22% UVA, 16% Solar) inks was seen in both UVA and solar experiments, demonstrating the consistency of the selfcleaning titania layer on ActivTM. The method presented provides a good solution for the high-throughput photocatalytic screening of a number of homogenous photocatalytically active materials simultaneously or numerous positions on a single film; both useful in assessing the homogeneity of a film or determining the best combination of reaction components to produce the optimum performance photocatalytic film

Atmospheric pressure chemical vapour deposition of boron doped titanium dioxide for photocatalytic water reduction and oxidation

Boron-doped titanium dioxide (B-TiO2) films were deposited by atmospheric pressure chemical vapour deposition of titanium(IV) chloride, ethyl acetate and tri-isopropyl borate on steel and fluorine-doped-tin oxide substrates at 500, 550 and 600 °C, respectively. The films were characterised using powder X-ray diffraction (PXRD), which showed anatase phase TiO2 at lower deposition temperatures (500 and 550 °C) and rutile at higher deposition temperatures (600 °C). X-ray photoelectron spectroscopy (XPS) showed a dopant level of 0.9 at% B in an O-substitutional position. The ability of the films to reduce water was tested in a sacrificial system using 365 nm UV light with an irradiance of 2 mW cm−2. Hydrogen production rates of B-TiO2 at 24 μL cm−2 h−1 far exceeded undoped TiO2 at 2.6 μL cm−2 h−1. The B-TiO2 samples were also shown to be active for water oxidation in a sacrificial solution. Photocurrent density tests also revealed that B-doped samples performed better, with an earlier onset of photocurrent

Simple method for the rapid simultaneous screening of photocatalytic activity over multiple positions of self-cleaning films

An intelligent ink, previously shown to be capable of rapidly assessing photocatalytic activity, was simply applied via a felt-pen onto a commercially available piece of Activ self-cleaning glass. The ink, comprising of redox dye resazurin and the sacrificial electron donor glycerol within an aqueous hydroxy ethyl cellulose (HEC) polymer media, was photocatalytically degraded in a two-step process. The key initial stage was the photo-reductive conversion of resazurin to resorufin, whereby a colour change from blue to pink occurred. The latter stage was the subsequent photo-reduction of the resorufin, where a slower change from pink to colourless was seen. Red and green components of red-green-blue colour extracted from flat-bed scanner digital images of resazurin ink coated photocatalytic films at intervals during the photocatalysis reaction were inversely proportional to the changes seen via UV-visible absorption spectroscopy and indicative of reaction kinetics. A 3 x 3 grid of intelligent ink was drawn onto a piece of Activ and a glass blank. The photocatalysis reaction was monitored solely by flat-bed digital scanning. Red-green-blue values of respective positions on the grid were extracted using a custom-built program entitled RGB Extractor. The program was capable of extracting a number of 5 x 5 pixel averages of red-green-blue components simultaneously. Allocation of merely three coordinates allowed for the automatic generation of a grid, with scroll-bars controlling the number of positions to be extracted on the grid formed. No significant change in red and green components for any position on the glass blank was observed; however, the Activ film displayed a homogenous photo-reduction of the dye, reaching maxima in red and minima in green components in 23 +/- 3 and 14 +/- 2 min, respectively. A compositionally graded N-doped titania film synthesised in house via a combinatorial APCVD reaction was also photocatalytically tested by this method where 247 positions on a 13 x 19 grid were simultaneously analysed. The dramatic variation in photocatalysis observed was rapidly quantified for all positions (2-3 hours) allowing for correlations to be made between thicknesses and N : Ti% compositions attained from Swanepoel and WDX analysis, respectively. N incorporation within this system was found to be detrimental to film activity for the photocatalysis reaction of intelligent ink under 365 nm light

Solid state metathesis: synthesis of metal carbides from metal oxides

Bulk reactions of transition metal oxides (V<sub>2</sub>O<sub>3</sub>, NaVO<sub>3</sub>, Nb<sub>2</sub>O<sub>5</sub>, LiNbO<sub>3</sub>, Ta<sub>2</sub>O<sub>5</sub>, LiTaO<sub>3</sub>, MoO<sub>3</sub>, Li<sub>2</sub>MoO<sub>4</sub> and Li<sub>2</sub>2WO<sub>4</sub>) with calcium and strontium carbides at 1000 degreesC for 12 h produce a range of transition metal carbides (V<sub>8</sub>C<sub>7</sub>, NbC, TaC, Mo<sub>2</sub>C and WC) in good yields (ca. 90%). The carbides were characterised by X-ray powder diffraction, scanning electron microscopy (SEM), energy dispersive analysis by X-rays (EDAX), electron probe, FTIR, microelemental analysis, transmission electron microscopy (TEM) and electron diffraction