High-performance gas sensors prepared using p-type oxide semiconductors such as NiO, CuO, Cr2O3, Co3O4, and Mn3O4 were reviewed. The ionized adsorption of oxygen on p-type oxide semiconductors leads to the formation of hole-accumulation layers (HALs), and conduction occurs mainly along the near-surface HAL. Thus, the chemoresistive variations of undoped p-type oxide semiconductors are lower than those induced at the electron-depletion layers of n-type oxide semiconductors. However, highly sensitive and selective p-type oxide-semiconductor-based gas sensors can be designed either by controlling the carrier concentration through aliovalent doping or by promoting the sensing reaction of a specific gas through doping/loading the sensor material with oxide or noble metal catalysts. The junction between p- and n-type oxide semiconductors fabricated with different contact configurations can provide new strategies for designing gas sensors. p-Type oxide semiconductors with distinctive surface reactivity and oxygen adsorption are also advantageous for enhancing gas selectivity, decreasing the humidity dependence of sensor signals to negligible levels, and improving recovery speed. Accordingly, p-type oxide semiconductors are excellent materials not only for fabricating highly sensitive and selective gas sensors but also valuable additives that provide new functionality in gas sensors, which will enable the development of high-performance gas sensors.

Highly sensitive and selective gas sensors using p-type oxide semiconductors: Overview

Gallium oxide (Ga2O3) is emerging as a viable candidate for certain classes of power electronics, solar blind UV photodetectors, solar cells, and sensors with capabilities beyond existing technologies due to its large bandgap. It is usually reported that there are five different polymorphs of Ga2O3, namely, the monoclinic (β-Ga2O3), rhombohedral (α), defective spinel (γ), cubic (δ), or orthorhombic (e) structures. Of these, the β-polymorph is the stable form under normal conditions and has been the most widely studied and utilized. Since melt growth techniques can be used to grow bulk crystals of β-GaO3, the cost of producing larger area, uniform substrates is potentially lower compared to the vapor growth techniques used to manufacture bulk crystals of GaN and SiC. The performance of technologically important high voltage rectifiers and enhancement-mode Metal-Oxide Field Effect Transistors benefit from the larger critical electric field of β-Ga2O3 relative to either SiC or GaN. However, the absence of clear demonstrations of p-type doping in Ga2O3, which may be a fundamental issue resulting from the band structure, makes it very difficult to simultaneously achieve low turn-on voltages and ultra-high breakdown. The purpose of this review is to summarize recent advances in the growth, processing, and device performance of the most widely studied polymorph, β-Ga2O3. The role of defects and impurities on the transport and optical properties of bulk, epitaxial, and nanostructures material, the difficulty in p-type doping, and the development of processing techniques like etching, contact formation, dielectrics for gate formation, and passivation are discussed. Areas where continued development is needed to fully exploit the properties of Ga2O3 are identified.

A review of Ga2O3 materials, processing, and devices

Xin Zhou,†,‡ Songyi Lee,† Zhaochao Xu,* and Juyoung Yoon*,† †Department of Chemistry and Nanoscience, Ewha Womans University, Seoul 120-750, Republic of Korea ‡Research Center for Chemical Biology, Department of Chemistry, Yanbian University, Yanjii 133002, People’s Republic of China Key Laboratory of Separation Science for Analytical Chemistry, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, 457 Zhongshan Road, Shahekou, Dalian, Liaoning, People’s Republic of China

Recent Progress on the Development of Chemosensors for Gases.

Improvements in the efficiency of combustion within a vehicle can lead to reductions in the emission of harmful pollutants and increased fuel efficiency. Gas sensors have a role to play in this process, since they can provide real time feedback to vehicular fuel and emissions management systems as well as reducing the discrepancy between emissions observed in factory tests and ‘real world’ scenarios. In this review we survey the current state-of-the-art in using porous materials for sensing the gases relevant to automotive emissions. Two broad classes of porous material – zeolites and metal–organic frameworks (MOFs) – are introduced, and their potential for gas sensing is discussed. The adsorptive, spectroscopic and electronic techniques for sensing gases using porous materials are summarised. Examples of the use of zeolites and MOFs in the sensing of water vapour, oxygen, NOx, carbon monoxide and carbon dioxide, hydrocarbons and volatile organic compounds, ammonia, hydrogen sulfide, sulfur dioxide and hydrogen are then detailed. Both types of porous material (zeolites and MOFs) reveal great promise for the fabrication of sensors for exhaust gases and vapours due to high selectivity and sensitivity. The size and shape selectivity of the zeolite and MOF materials are controlled by variation of pore dimensions, chemical composition (hydrophilicity/hydrophobicity), crystal size and orientation, thus enabling detection and differentiation between different gases and vapours.

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Gas sensing using porous materials for automotive applications

Metal-oxide-semiconductor (MOS) based gas sensors have been considered a promising candidate for gas detection over the past few years. However, the sensing properties of MOS-based gas sensors also need to be further enhanced to satisfy the higher requirements for specific applications, such as medical diagnosis based on human breath, gas detection in harsh environments, etc. In these fields, excellent selectivity, low power consumption, a fast response/recovery rate, low humidity dependence and a low limit of detection concentration should be fulfilled simultaneously, which pose great challenges to the MOS-based gas sensors. Recently, in order to improve the sensing performances of MOS-based gas sensors, more and more researchers have carried out extensive research from theory to practice. For a similar purpose, on the basis of the whole fabrication process of gas sensors, this review gives a presentation of the important role of screening and the recent developments in high throughput screening. Subsequently, together with the sensing mechanism, the factors influencing the sensing properties of MOSs involved in material preparation processes were also discussed in detail. It was concluded that the sensing properties of MOSs not only depend on the morphological structure (particle size, morphology, pore size, etc.), but also rely on the defect structure and heterointerface structure (grain boundaries, heterointerfaces, defect concentrations, etc.). Therefore, the material-sensor integration was also introduced to maintain the structural stability in the sensor fabrication process, ensuring the sensing stability of MOS-based gas sensors. Finally, the perspectives of the MOS-based gas sensors in the aspects of fundamental research and the improvements in the sensing properties are pointed out.

Metal-oxide-semiconductor based gas sensors: screening, preparation, and integration

Single-source precursors to gallium and indium oxide thin films

In2O3 and In2O3:M (M = Ti or Ta) thin films were deposited on glass substrates via aerosol-assisted chemical deposition (AACVD) at 450 °C. The resulting films were characterized by a range of techniques including glancing-angle X-ray diffraction, scanning electron microscopy, wavelength dispersive analysis of X-rays, and optical transmission/reflectance studies to investigate the effect of doping on the films. The In2O3:M thin films were found to contain 6.5 and 2.3 at.% of Ti and Ta, respectively. The gas sensing properties were investigated on films deposited onto gas sensing substrates via AACVD. Tantalum doped indium oxide (In2O3:Ta) thin films showed a superior response, compared to In2O3, to a number of reducing gases (ethanol, CO, ammonia) and also the oxidizing gas NO2. Considerable selectivity to ethanol was observed; the greatest gas response (R/R0) was 16.95 to 100 ppm ethanol.

Tantalum and Titanium doped In2O3 Thin Films by Aerosol-Assisted Chemical Vapor Deposition and their Gas Sensing Properties

Terrorists frequently use explosives and they represent an imminent threat to national and global security. Recent events highlight the necessity of explosive detection, demonstrating the need for developing and applying new sensors for explosive gas detection. Semiconducting metal oxide gas sensors can be incorporated into electronic noses, which provide a cheap, portable and highly sensitive device. Using unmodified, admixed and 2-layered sensors consisting of WO3 and chromium titanium oxide (CTO), an array of seven heterojunction semiconducting metal oxide sensors was produced. All seven sensors were tested against four gases associated with explosive materials. The sensitivity was improved by using 2-layered sensors in response to ethanol, ammonia and nitromethane, whereas the admixed sensors showed high sensitivity when exposed to nitrogen dioxide. The selectivity of the array of sensors was tested using machine-learning techniques with a support vector machine. The technique produced good data classification when classifying the gases used within the study.

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An array of WO3 and CTO heterojunction semiconducting metal oxide gas sensors used as a tool for explosive detection

The illicit manufacture of drugs in the 21st century presents a danger to first responders, bystanders and the environment, making its detection important. Electronic noses based on metal oxide semiconducting (MOS) sensors present a potential technology to create devices for such purposes. An array of four thick film MOS gas sensors was fabricated, based on zinc oxide inks. Production took place using a commercially available screen printer, a 3 × 3 mm alumina substrate containing interdigitated electrodes and a platinum heater track. ZnO inks were modified using zeolite β, zeolite Y and mordenite admixtures. The sensors were exposed to four gases commonly found in the clandestine laboratory environment; these were nitrogen dioxide, ethanol, acetone and ammonia. Zeolite modification was found to increase the sensitivity of the sensor, compared to unmodified ZnO sensors, all of which showed strong responses to low ppm concentrations of acetone, ammonia and ethanol and to ppb concentrations of nitrogen dioxide. Machine learning techniques were incorporated to test the selectivity of the sensors. A high level of accuracy was achieved in determining the class of gas observed.

The gas sensing properties of zeolite modified zinc oxide

Bis(β-ketoimine) ligands, [R{N(H)C(Me)-CHC(Me)═O}(2)] (L(1)H(2), R = (CH(2))(2); L(2)H(2), R = (CH(2))(3)), linked by ethylene (L(1)) and propylene (L(2)) bridges have been used to form aluminum, gallium, and indium chloride complexes [Al(L(1))Cl] (3), [Ga(L(n))Cl] (4, n = 1; 6, n = 2) and [In(L(n))Cl] (5, n = 1; 7, n = 2). Ligand L(1) has also been used to form a gallium hydride derivative [Ga(L(1))H] (8), but indium analogues could not be made. β-ketoimine ligands, [Me(2)N(CH(2))(3)N(H)C(R')-CHC(R')═O] (L(3)H, R' = Me; L(4)H, R' = Ph), with a donor-functionalized Lewis base have also been synthesized and used to form gallium and indium alkyl complexes, [Ga(L(3))Me(2)] (9) and [In(L(3))Me(2)] (10), which were isolated as oils. The related gallium hydride complexes, [Ga(L(n))H(2)] (11, n = 3; 12, n = 4), were also prepared, but again no indium hydride species could be made. The complexes were characterized mainly by NMR spectroscopy, mass spectrometry, and single crystal X-ray diffraction. The β-ketoiminate gallium hydride compounds (8 and 11) have been used as single-source precursors for the deposition of Ga(2)O(3) by aerosol-assisted (AA)CVD with toluene as the solvent. The quality of the films varied according to the precursor used, with the complex [Ga(L(1))H] (8) giving by far the best quality films. Although the films were amorphous as deposited, they could be annealed at 1000 °C to form crystalline Ga(2)O(3). The films were analyzed by powder XRD, SEM, and EDX.

David Pugh

Papers

Single-source precursors to gallium and indium oxide thin films

Tantalum and Titanium doped In2O3 Thin Films by Aerosol-Assisted Chemical Vapor Deposition and their Gas Sensing Properties

An array of WO3 and CTO heterojunction semiconducting metal oxide gas sensors used as a tool for explosive detection

The gas sensing properties of zeolite modified zinc oxide

Group 13 β-ketoiminate compounds: gallium hydride derivatives as molecular precursors to thin films of Ga2O3.