The light-enhanced NO₂ sensing properties of porous silicon gas sensors at room temperature

The NO2 gas sensing behavior of porous silicon(PS) is studied at room temperature with and without ultraviolet(UV) light radiation.The PS layer is fabricated by electrochemical etching in an HF-based solution on a p +-type silicon substrate.Then,Pt electrodes are deposited on the surface of the PS to obtain the PS gas sensor.The NO2 sensing properties of the PS with different porosities are investigated under UV light radiation at room temperature.The measurement results show that the PS gas sensor has a much higher response sensitivity and faster response-recovery characteristics than NO2 under the illumination.The sensitivity of the PS sample with the largest porosity to 1 ppm NO2 is 9.9 with UV light radiation,while it is 2.4 without UV light radiation.We find that the ability to absorb UV light is enhanced with the increase in porosity.The PS sample with the highest porosity has a larger change than the other samples.Therefore,the effect of UV radiation on the NO2 sensing properties of PS is closely related to the porosity.     

Investigations on Pd:SnO2/porous silicon structures for sensing LPG and NO2 gas

P-type porous silicon (PS) structure has been prepared by anodic electrochemical etching process under optimized conditions. Photoluminescence studies of the PS structure show emission at longer wavelengths (red) for the excitation at 365 nm. Scanning electron microscope investigations of the PS surface confirm the formation of uniform porous structure, and the pore diameter have been estimated as 25 μm. Pd:SnO₂/PS/p-Si heterojunction with top gold ohmic contact developed by conventional methods has been used as the sensor device. Sensing properties of the device towards liquefied petroleum gas (LPG) and NO₂ gas have been investigated in an indigenously developed sensor test rig. The response and recovery characteristics of the sensor device at different operating temperatures show short response time for LPG. From the studies, maximum sensitivity and optimum operating temperature of the device towards LPG and NO₂ gas sensing has been estimated as 69% at 180 °C and 52% at 220 °C, respectively. The developed sensor device shows a short response time of 25 and 57 s for sensing LPG and NO₂ gases, respectively. Paper presented at the Third International Conference on Ionic Devices (ICID 2006), Chennai, Tamilnadu, India, Dec. 7–9, 2006.     

Temperature dependence of NO2 sensitivity of YSZ-based mixed potential type sensor attached with NiO sensing electrode

A mixed potential type yttria-stabilized zirconia-based sensor using NiO sensing electrode and Pt reference electrode was fabricated, and its NO₂ sensing characteristics were examined at various operating temperatures in the range of 700–950 °C. It was observed that the sensitivity to NO₂ strongly depends on the operating temperature of the sensor; the sensitivity decreases with increasing operating temperature, while the response/recovery rates increase. To rationalize this temperature dependence of NO₂ response, polarization curves and complex impedances of the sensor were measured in the base gas and in the sample gas (400 ppm NO₂?+?base gas) at various operating temperatures. It turned out that the operating temperature had a strong influence on the rate of anodic reaction of oxygen; the increased rate of anodic reaction leads to lower NO₂ sensitivity and quicker response/recovery at higher operating temperature.     

UV-enhanced room-temperature gas sensing of ZnGa2O4 nanowires functionalized with Au catalyst nanoparticles

ZnGa₂O₄ nanowires were synthesized using a thermal evaporation technique. Scanning electron microscopy, transmission electron microscopy, and X-ray diffraction revealed that the nanowires were single crystals 30–200 nm in diameter and ranged up to ～100 μm in length. The sensing properties of multiple networked ZnGa₂O₄ nanowire sensors functionalized with Au catalyst nanoparticles with diameters of a few nanometers toward NO₂ gas at room temperature under UV irradiation were examined. The sensors showed a remarkably enhanced response and far reduced response and recovery times toward NO₂ gas at room temperature under 254 nm-ultraviolet (UV) illumination. The response of ZnGa₂O₄ nanowires to NO₂ gas at room temperature increased from ～100 to ～861 % with increasing the UV intensity from 0 to 1.2 mW/cm². The significant improvement in the response of ZnGa₂O₄ nanowires to NO₂ gas by UV irradiation is attributed to the increased change in resistance due to the increase in the number of electrons participating in the reactions with NO₂ molecules by photo-generation of electron–hole pairs.     

氧化钨纳米线-单壁碳纳米管复合型气敏元件的室温NO2敏感性能与机理

利用溶剂热法合成了一维的氧化钨纳米线, 通过掺入适量单壁碳纳米管(SWNT)制备了基于氧化钨纳米线-SWNT 复合结构的室温气敏元件并评价了其对NO₂气体的室温敏感性能. 利用X射线与扫描电子显微镜表征了材料的微结构, 结果表明, 合成的氧化钨纳米线具有单斜的W₁₈O₄₉结构, 复合材料中SWNT被包埋在氧化钨纳米线中间. 气敏性能测试结果表明, 氧化钨纳米线-SWNT复合结构气敏元件在室温下对NO₂气体表现出了高的灵敏度和超快的响应特性; 较低的SWNT掺入量对获得好的气敏性能有利. 分析了基于复合结构材料气敏元件的可能的气敏机理, 认为元件良好的室温敏感性能与SWNT掺入在复合结构材料中引入大量的贯穿气孔和p-n异质结有关.     

UV-activated gas sensing properties of ZnS nanorods functionalized with Pd

Pd-functionalized ZnS nanorods were prepared for use as gas sensors. Scanning electron microscopy revealed the diameters and lengths of the nanorods ranging from 30 to 80 nm and from 2 to 5 μm, respectively. The diameter of Pd nanoparticles ranged from 2 to 5 nm. Transmission electron microscopy revealed that ZnS nanorods and Pd nanoparticles were monocrystalline and amorphous, respectively. The responses of multiple networked ZnS nanorods sensors to 1–5 ppm NO₂ were increased substantially by a combination of Pd functionalization and UV irradiation. Pristine ZnS nanorod sensors at room temperature in the dark showed a response (∼100%) almost independent of NO₂ concentration in a NO₂ concentration range of 1–5 ppm. Pristine ZnS nanorod sensors showed enhanced responses of 214–603% to 1–5 ppm NO₂ at room temperature under UV illumination. Pd-functionalized ZnS nanorods sensors showed further enhanced responses of 355–1511% to 1–5 ppm NO₂ at room temperature under UV illumination. The NO₂ gas sensing mechanism of the Pd-functionalized ZnS nanorods sensors under UV illumination is discussed in depth.     

Spatial distribution and formation of nitrate radical NO<Stack><Subscript>3</Subscript><Superscript>2−</Superscript></Stack> in Antarctic calcitic evaporates

Nitrate radical NO₃²⁻ in calcitic evaporate was discovered in Antarctica. The distribution and formation of nitrate radical NO₃²⁻ in the calcite have been studied by pulse and continuous-wave electron spin resonance. In samples that had been annealed to destroy the NO₃²⁻, regeneration of the radical by γ-rays or UV light indicated that the radical was formed by UV light (with wavelengths less than 340 nm) from solar rays, not by environmental radiation. The nonuniform spatial distribution of the nitrate radical, which was deduced from high ratios of local spin density to total spin density, suggests that the nitrate impurity was introduced into the calcium carbonate after carbonate grain formation. Formation of the carbonate-containing nitrate requires the presence of high amounts of nitrate and a dry climate. Formation of the nitrate radical requires sample exposure to UV light. These conditions are satisfied in the environment of Antarctica.     

Synthesis and room-temperature NO_2 gas sensing properties of a WO_3 nanowires/porous silicon hybrid structure

We report on the fabrication and performance of a room-temperature NO2 gas sensor based on a WO3 nanowires/porous silicon hybrid structure. The W18O49 nanowires are synthesized directly from a sputtered tungsten film on a porous silicon （PS） layer under heating in an argon atmosphere. After a carefully controlled annealing treatment, WO3 nanowires are obtained on the PS layer without losing the morphology. The morphology, phase structure, and crystallinity of the nanowires are investigated by using field emission scanning electron microscopy （FESEM）, X-ray diffractometer （XRD）, and high-resolution transmission electron microscopy （HRTEM）. Comparative gas sensing results indicate that the sensor based on the WO3 nanowires exhibits a much higher sensitivity than that based on the PS and pure WO3 nanowires in detecting NO2 gas at room temperature. The mechanism of the WO3 nanowires/PS hybrid structure in the NO2 sensing is explained in detail.     

Synthesis and gas sensing properties of high porosity n-type nickel ferrite thin film assisted by altering magnetic field

NiFe₂O₄ thin film with high porosity based gas sensors had been prepared and their microstructure and gas sensing property were investigated. The sensing layer, consisted of perpendicular overlapped NiFe₂O₄ chains which were induced by altering magnetic field to self-assemble, had high porosity. The phase character and porous microstructure were characterized by X-ray diffraction (XRD) and a polarizing optical microscopy. The gas sensing tests results indicated that the sensor presented a high sensitivity to NH₃ at 150 °C, and was selective to NH₃ below 200 °C. The large porosity microstructure should benefit the reaction between target gas and sensing material and the detection of low concentration gas at low working temperature. In repeatability tests, the response and recovery time values had only narrow fluctuations.     

Mixed-potential-type NOx sensor based on YSZ and zinc oxide sensing electrode

Electrochemical sensors using tubular yttria-stabilized zirconia (YSZ) and oxide sensing electrode (SE) were fabricated and examined for NO_x detection at high temperatures. The mixed-potential-type NO_x sensor using ZnO-SE gave the highest sensitivity to NO_x among other single-type oxides tested as SEs in the temperature range of 600–700 °C. The response of the ZnO-attached device was a linear for the logarithm of NO₂ (NO) concentrations from 40 to 450 ppm. The sensing mechanism of the sensor was discussed on the basis of the gas adsorption-desorption behavior, the catalytic activity data, and electrochemical behavior for oxides examined.     

Deposition and microstructure characterization of atmospheric plasma-sprayed ZnO coatings for NO2 detection

This work studied the possibility of using a sensor based on plasma-sprayed zinc oxide (ZnO) sensitive layer for NO₂ detection. The atmospheric plasma spray process was employed to deposit ZnO gas sensing layer and the obtained coating structure was characterized by scanning electron microscopy and X-ray diffraction analysis. The influences of gas concentration, working temperature, water vapor in testing air on NO₂ sensing performance of the ZnO sensors were studied. ZnO sensors showed a good sensor response and selectivity to NO₂ at an optimal working temperature.     

Graphene-based nitrogen dioxide gas sensors

In this study, we demonstrated that graphene could selectively absorb/desorb NO_x molecules at room temperature. Chemical doping with NO₂ molecules changed the conductivity of the graphene layers, which was quantified by monitoring the current–voltage characteristics at various NO₂ gas concentrations. The adsorption rate was found to be more rapid than the desorption rate, which can be attributed to the reaction occurred on the surface of the graphene layer. The sensitivity was 9% when an ambient of 100 ppm NO₂ was used. Graphene-based gas sensors showed fast response, good reversibility, selectivity and high sensitivity. Optimization of the sensor design and integration with UV-LEDs and Silicon microelectronics will open the door for the development of nano-sized gas sensors that are extremely sensitive.     

UV-LED Photo-activated Chemical Gas Sensors: A Review

Metal oxide semiconductor gas sensors operating under UV irradiation have been validated for detection of variety of chemicals in wide ranges of concentrations at room temperature. This article reviews recent advances in UV-activated metal oxide gas sensors in general and outlines the operating principles and sensing performance of UV-LED based sensors in particular. The sensing properties of several metal oxide semiconductors such as ZnO, TiO₂, SnO₂, In₂O₃, and metal oxide composites under UV-LED irradiation are individually presented and their advantages and shortcomings toward various gases are compared. Moreover, it is demonstrated that for the UV-LED based gas sensors, the performance can be improved by optimizing the sensor platform design and UV source parameters such as wavelength and power intensity. Further, it is illustrated that the gas sensing selectivity can be tuned by modifying the semiconductor layer structure or adjusting appropriate wavelength to an optimal value.     

p-type porous-silicon transducer for cation detection: effect of the porosity, pore morphology, temperature and ion valency on the sensor response and generalisation of the Nernst equation

This paper shows the possibility of using oxidised porous silicon (PS) as a transducer material for ion-sensor applications. It aims to study the over-Nernstian behaviour of the porous electrodes towards the concentration of cations in contact. The dependence of the sensitivity on the porosity of the samples prepared from highly doped substrates has been studied. Maximal values of over-Nernstian sensitivities around 240 mV/pNa and ∼92 mV/pCu, corresponding to a PS-layer porosity of about 65%, obtained respectively from p⁻ and p⁺ silicon substrates, have been registered. Furthermore, the effect of the porous nanostructure morphology has been studied, by preparing PS samples from weakly doped wafers. The porous-silicon-based sensor behaviour for different PS-layer thicknesses has also been experimentally investigated. According to these results, a physical model has been proposed to explain the mechanisms which govern the charge-carrier transfer from one side to the other of the functionalised oxide layer, and leads to the over-Nernstian adsorption of the cationic species at the electrolyte/SiO₂ interface. Afterwards, the Nernst relation has been generalised accordingly, on one hand, to the previous experimental results, and on the other hand, to the results obtained about the ion-valency and the electrolyte-temperature effects on the sensor responses. Received: 15 December 2000 / Accepted: 18 December 2000 / Published online: 23 March 2001     

Preparation of WO3 nanoparticles and application to NO2 sensor

WO₃ nanoparticles were prepared by evaporating tungsten filament under a low pressure of oxygen gas, namely, by a gas evaporation method. The crystal structure, morphology, and NO₂ gas sensing properties of WO₃ nanoparticles deposited under various oxygen pressures and annealed at different temperatures were investigated. The particles obtained were identified as monoclinic WO₃. The particle size increased with increasing oxygen pressure and with increasing annealing temperature. The sensitivity increased with decreasing particle size, irrespective of the oxygen pressure during deposition and annealing temperature. The highest sensitivity of 4700 to NO₂ at 1 ppm observed in this study was measured at a relatively low operating temperature of 50 °C; this sensitivity was observed for a sensor made of particles as small as 36 nm.     

Fiber-Optic Chemical Sensor for Detection of NO2 Using Poly (3-Octylthiophene)

Abstract

A fiber-optic chemical sensor (FOCS) for detection of nitrogen dioxide (NO ₂ ) molecules is reported. The FOCS presents an optropode structure because of the transmission properties of the sensitive material. The NO ₂ FOCS is activated by using the semiconductor polymer: regioregular head-to-tail poly(3-octylthiophene-2,5-diyl). The operation wavelength of the sensor is 543.5 nm such that a simple LED and detector can be used for the design of this device. The sensor response decreases after each exposure, demonstrating the reduction in sensitivity as well as irreversibility lower than 5%. However, its properties such as rapid response, high selectivity, high sensitivity (0.43 ± 0.01 muW/ppm), hygroscopic properties, and its operation at room temperature make this kind of FOCS a good alternative for NO ₂ toxic gas detection.     

n型有序多孔硅基氧化钨室温气敏性能研究

利用电化学腐蚀方法制备了n型有序多孔硅, 并以此为基底用直流磁控溅射法在其表面溅射不同厚度的氧化钨薄膜. 利用X射线和扫描电子显微镜表征了材料的成分和结构, 结果表明, 多孔硅的孔呈柱形有序分布, 溅射10 min的WO₃薄膜是多晶结构, 比较松散地覆盖在整个多孔硅的表面. 分别测试了多孔硅和多孔硅基氧化钨在室温条件下对二氧化氮的气敏性能, 结果表明, 相对于多孔硅, 多孔硅基氧化钨薄膜对二氧化氮的气敏性能显著提高. 对多孔硅基氧化钨复合结构的气敏机理分析认为, 多孔硅和氧化钨薄膜复合形成的异质结对良好的气敏性能起到主要作用, 氧化钨薄膜表面出现了反型层引起了气敏响应时电阻的异常变化. 关键词： 有序多孔硅 氧化钨薄膜 二氧化氮 室温气敏性能     

Recovery properties of hydrogen gas sensor with Pd/titanate and Pt/titanate nanotubes photo-catalyst by UV radiation from catalytic poisoning of H2S

Recovery properties after H₂S catalytic poisoning of catalytic-type gas sensor with photo-catalysts and UV radiation have been examined. Each sensing material of the sensor consists of Pd, Pt supported on γ-Al₂O₃ and Pd/titanate, Pt/titanate nanotubes or TiO₂ particles. Pd/titanate and Pt/titanate nanotubes photo-catalyst were synthesized by hydrothermal synthesis method. All the sensors were deactivated after 500 ppm H₂S exposure for 20 h. The sensors with Pd/titanate or Pt/titanate nanotubes showed regenerated voltage response under UV radiation. However the sensor with TiO₂ particles showed negligible regenerated voltage response. Regenerated voltage response with Pd/titanate or Pt/titanate nanotubes may stem from location of Pd or Pt catalyst on the titanate nanotube photo-catalyst.     

Enhanced physical properties of porous silicon for improved hydrogen gas sensing

In the current communication, porous silicon samples were prepared by pulsed photoelectrochemical etching using a hydrofluoric acid-based solution. The structural and gas-sensing properties of the samples were studied. Apart from the cycle time T and pause time T_off of the pulsed current, a novel parameter, in the shape of the current named ‘delay time T_d’ was introduced. Our results showed that by optimization of delay time, the porosity of samples can be controlled due to the chemical preparation of silicon surface prior to electrochemical anodization. The fourier-transform infrared measurements of porous silicon (PS) layers on Si substrate showed that the typical PS surface was characterized by chemical species like Si–H and Si–O–Si terminations. The two-minute delay before applying electrical current was considered sufficient for the fabrication of higher porosity (83%), more uniform, and more stable structures. The photoluminescence (PL) peak of the optimized sample showed higher intensity than the other samples. An obvious PL blue shift also revealed a change in the crystallographic characteristics of silicon due to quantum confinement effects. Metal–semiconductor–metal diodes with Schottky contacts of nickel were fabricated on PS samples and the potential application of optimized substrates for the improved sensitivity, stability, response time and recovery time of hydrogen gas sensors was subsequently studied.     

Room-temperature gas sensors based on gallium nitride nanoparticles

Room-temperature sensing characteristics for H₂, ethanol, NH₃, H₂S and water have been investigated with thick-film sensors based on GaN nanoparticles, prepared by a simple chemical route. In general, GaN nanoparticles exhibit satisfactory sensor properties for these gases and vapors even at room temperature. The sensitivity for ethanol is found to be highest, the sensitivity and recovery times being smallest. Gas sensor properties of GaN seem to be related to intrinsic defects, which act as sorption sites for the gas molecules.