Russell Binions

Metal Oxide Semi-Conductor Gas Sensors in Environmental Monitoring

Metal oxide semiconductor gas sensors are utilised in a variety of different roles and industries. They are relatively inexpensive compared to other sensing technologies, robust, lightweight, long lasting and benefit from high material sensitivity and quick response times. They have been used extensively to measure and monitor trace amounts of environmentally important gases such as carbon monoxide and nitrogen dioxide. In this review the nature of the gas response and how it is fundamentally linked to surface structure is explored. Synthetic routes to metal oxide semiconductor gas sensors are also discussed and related to their affect on surface structure. An overview of important contributions and recent advances are discussed for the use of metal oxide semiconductor sensors for the detection of a variety of gases—CO, NOx, NH3 and the particularly challenging case of CO2. Finally a description of recent advances in work completed at University College London is presented including the use of selective zeolites layers, new perovskite type materials and an innovative chemical vapour deposition approach to film deposition.

Gas sensing with nano-indium oxides (In2O3) prepared via continuous hydrothermal flow synthesis.

A rapid, clean, and continuous hydrothermal route to the synthesis of ca. 14 nm indium oxide (In(2)O(3)) nanoparticles using a superheated water flow at 400 °C and 24.1 MPa as a crystallizing medium and reagent is described. Powder X-ray diffraction (XRD) of the particles revealed that they were highly crystalline despite their very short time under hydrothermal flow conditions. Gas sensing substrates were prepared from an In(2)O(3) suspension via drop-coating, and their gas sensing properties were tested for response to butane, ethanol, CO, ammonia, and NO(2) gases. The sensors showed excellent selectivity toward ethanol, giving a response of 18-20 ppm.

Advances in thermochromic vanadium dioxide films

Vanadium dioxide is a thermochromic material that undergoes a semiconductor to metal transitions at a critical temperature of 68 °C. This phase change from a low temperature monoclinic structure to a higher temperature rutile structure is accompanied by a marked change in infrared reflectivity and change in resistivity. This review presents the fundamental chemical principles that describe the electronic structure and properties of solids, and the chronological developments in the theory behind the thermochromic transitions such as, the effects of electron–electron interactions and structural phase changes due to lattice distortions. An extensive discussion and observations on the current understanding of the nature of the semiconductor-to-metal transition exhibited by vanadium dioxide is detailed. The possibility of manipulating the transition temperature by introducing various dopants, additional layers or by size effects into the vanadium dioxide lattice are examined. Thermochromic vanadium dioxide materials may be exploited in areas such as microelectronics, data storage, or intelligent architectural glazing, thus are required to be synthesised as thin films for use in such applications. The numerous synthetic techniques (physical vapour deposition, sol–gel method, pulsed laser deposition, chemical vapour deposition), for making metal oxide thermochromic thin films are described in reference to the production of vanadium dioxide with a particular focus on recent results.

Doped and un-doped vanadium dioxide thin films prepared by atmospheric pressure chemical vapour deposition from vanadyl acetylacetonate and tungsten hexachloride: the effects of thickness and crystallographic orientation on thermochromic properties

The atmospheric pressure chemical vapour deposition reaction of vanadyl acetylacetonate and tungsten hexachloride with oxygen led to the production of thin films of tungsten doped monoclinic vanadium dioxide on glass substrates. Scanning electron microscopy and X-ray diffraction indicated that the films had different morphologies and crystallinities depending on the deposition conditions used. Transmission and reflectance measurements showed a significant change in properties in the near infra-red either side of the metal to semiconductor transition. Variable temperature transmission studies show that the metal to semiconductor transition was lowered by tungsten doping. The effect of film thickness was studied with un-doped and doped films. It was found that film thickness limited the intensity of light passing through the film and the extent of the thermochromic transition but was found not to influence the hysteresis width or temperature of transition. Different film growth conditions led to a range of film morphologies which profoundly affected the resulting optical properties of the films. It was found that film morphology and preferred crystallographic orientation had a marked influence on the width and switching temperature of the thermochromic transition.

Thin films for solar control applications

The excessive use of heating systems in cold climates and air conditioning systems in hotter climates is resulting in the extensive use of electricity in order to maintain such systems. This in turn leads to the greater use of fossil fuels and higher emissions of carbon dioxide and other pollutant gases. The growing amount of carbon dioxide emissions is contributing to the problem of global warming, hence increasing the need for alternative technologies to heating and air conditioning systems. One such alternative is the production of thin films which can be used as window glazing coatings to construct ‘smart windows’. These windows have the greatest use within constant climates. In cold climates, windows with high solar transmittance and low thermal emittance are needed; this allows sunlight into the building to brighten the room but stops heat from escaping thus warming the room. In constantly hot climates, materials that are transparent in the visible region but reflective in the infrared, such as thin metallic coatings, can be used to ensure that the inside of the building remains cool. These solar control coatings, however, pose a problem in varying climates such as in northern and central Europe. For these cases, materials that have altering properties owing to external surroundings could be the solution. These ‘chromatic’ materials include several categories, such as photochromic glasses and polymers, thermochromic metal oxides and electrochromic materials. This review will begin with a discussion as to the chemistry behind the solar control coatings and chromic materials including ambient radiation and the ideal of a black-body object. It will then look in depth at each class of these chromic materials considering experimental results and theoretical insight as well as production techniques and applications.

Highly Sensitive ZnO Nanorod- and Nanoprism-Based NO2 Gas Sensors: Size and Shape Control Using a Continuous Hydrothermal Pilot Plant

Continuous hydrothermal flow synthesis of crystalline ZnO nanorods and prisms is reported via a new pilot-scale continuous hydrothermal reactor (at nominal production rates of up to 1.2 g/h). Different size and shape particles of ZnO (wurtsite structure) were obtained via altering reaction conditions such as the concentration of either additive H2O2 or metal salt. Selected ZnO samples (used as prepared) were evaluated as solid oxide gas sensors, showing excellent sensitivity toward NO2 gas. It was found that both the working temperature and gas concentration significantly affected the NO2 gas response at concentrations as low as 1 ppm.

Zeolite-Modified Discriminating Gas Sensors

The use of zeolites as transformation layers to enhance the response and discriminating power of solid-state metal-oxide-semiconductor gas sensors is demonstrated. Thick film sensors were prepared by screen printing layers of tungsten trioxide or chromium titanium oxide with various zeolites as overlayers. The sensors gas response was tested against carbon monoxide and ethanol in varying concentrations. Experimental result.,; show that it is possible to dramatically alter the response behavior of the devices: in the instance of ethanol gas with a zeolite Y-modified sensor. the response was increased by 2 orders of magnitude compared to the unmodified sensor. Computational modelling studies show that a combination of catalytic reaction and diffusion behavior are responsible for these changes. Such discriminatory behavior should prove useful in electronic noses and sensor arrays. (c) 2009 The Electrochemical Society. [DOI: 10.1149/1.3065436] All rights reserved.

Thermochromic Coatings for Intelligent Architectural Glazing

Thermochromic glazing is a type of intelligent glazing; one where the properties of the glazing change according to some external stimulus. More particularly a thermochromic window is a device that changes its transmission and reflectance properties at a critical temperature (Tc). Atthis specific temperature the material undergoes a semi-conductor to metal transition. At temperatures lower than Tc the window lets all of the solar energy that hits it through. At emperatures above Tc the window reflects the infra-red portion of solar energy. In such a way thermochromic windows may help reduce air conditioning and heating costs leading to more energy efficient buildings. This review details the nature of the semi-conductor to metal transition and indicates how substitutional doping within a crystal lattice can be used to manipulate and fine tune the critical temperature. Also detailed is the underlying science and methodologies so far employed in the production of thermochromic thin films.

Graphene/nitrogen-doped porous carbon sandwiches for the metal-free oxygen reduction reaction: conductivity versus active sites

The oxygen reduction reaction (ORR) plays a critical role in sustainable energy systems. Among the most promising metal free ORR electrocatalysts, nitrogen-doped carbon materials have generated significant research interest. Nitrogen doping within a graphitic/turbostratic network of carbon atoms generates active sites for the ORR via C–N bond polarisation that induces a reduced energy barrier towards the ORR on the adjacent carbon atom. At the same time, nitrogen doping leads to an increased electrical conductivity due to electron excess in the delocalised π-system. Thus, the electrical conductivity and the number and the nature of the active sites are two important factors determining the performance of nitrogen-doped carbons in the ORR. Herein, N-doped nanocarbon/graphene composites were carefully designed, synthesized, characterized and tested as electrocatalysts in the ORR in order to decouple these two factors and investigate the underlying relationships between them. Chitosan was used as a nitrogen precursor for nanocarbon, while reduced graphene oxide was introduced to tune the electrical conductivity. Our results show that a low conductivity limits the exertion of active sites and results in a conductivity-dependent ORR activity. However, when the conductivity reaches a critical value, the active sites can be fully utilized and contribute to a positively correlated ORR activity.

Nanostructured tungsten oxide gas sensors prepared by electric field assisted aerosol assisted chemical vapour deposition

Nanostructured thin films of tungsten trioxide were deposited on to gas sensor substrates at 600 °C from the aerosol assisted chemical vapour deposition reaction of tungsten hexaphenoxide solutions in toluene under the influence of electric fields. The electric fields were generated by applying a potential difference between the inter-digitated electrodes of the gas sensor substrates during the deposition. The deposited films were characterised using scanning electron microscopy, X-ray diffraction and Raman spectroscopy. The application of an electric field, encouraged formation of enhanced nanostructured morphologies, with an increase in needle length and reduction in needle diameter being observed. The film gas sensor properties were also examined; it was found that the highest response of 110 to 800 ppb NO2 was given by a sensor grown under the influence of a 1.8 × 104 V m−1 electric field and operated at 250 °C, a 2.5 times enhancement compared to a sensor grown in the absence of an electric field under its optimal operating conditions.