Single and networked CuO nanowires for highly sensitive p‐type semiconductor gas sensor applications

Development of high‐performance p‐type semiconductor based gas sensors exhibiting fast‐response/recovery times with ultra‐high response are of major importance for gas sensing applications. Recent reports demonstrated the excellent properties of p‐type semiconducting oxide for various practical applications, especially for selective oxidation of volatile organic compounds (VOCs). In this work, sensors based on CuO nanowire (NW) networks have been successfully fabricated via a simple thermal oxidation process on pre‐patterned Au/Cr pads. Our investigation demonstrates high impact of the process temperature on aspect ratio and density of copper oxide NWs. An optimal temperature for growth of thin and densely packed NWs was found to be at 425 °C. The fabricated sensors demonstrated ultra‐high gas response by a factor of 313 to ethanol vapour (100 ppm) at an operating temperature of 250 °C. High stability and repeatability of these sensors indicate the efficiency of p‐type oxide based gas sensors for selective detection of VOCs. A high‐performance nanodevice was fabricated in a FIB‐SEM system using a single CuO NW, demonstrating an ethanol response of 202 and rapid response and recovery of ～198 ms at room temperature. The involved gas sensing mechanism of CuO NW networks has been described. We consider that the presented results will be of a great interest for the development of higher‐performance p‐type semiconductor based sensors and bottom‐up nanotechnologies. (© 2016 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

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.     

Highly sensitive and selective trimethylamine sensors based on WO3 nanorods decorated with Au nanoparticles

One-dimensional tungsten oxide (WO₃) gas sensing materials have been widely used for the detection of trimethylamine (TMA) gas. Furthermore, it is believed that an effective method to improve the gas sensing performance is to introduce noble metals into sensing materials. In this work, a novel gas sensing material was prepared by decorating Au nanoparticles on WO₃ nanorods. Based on field emission scanning electron microscopy (FESEM/EDS), X-ray diffraction (XRD), and transmission electron microscopy (TEM), the morphology and microstructure of as-prepared samples were characterized. Results show that Au nanoparticles with diameter of 13–15 nm are loaded on the surface of WO₃ nanorods with length of about 1–2 µm and width of 50–80 nm. Gas sensing tests reveal that the Au@WO₃ sensor has remarkably enhanced response to TMA gas compared with pure WO₃ nanorods. In addition, and the gas sensing mechanism has been investigated based on the experimental results. The superior sensing features indicate the present Au@WO₃ nanocomposites are promising for gas sensors, which can be used in the detection of the trimethylamine gas and this work provides insights and strategies for the fabrication of sensing materials.     

Formation of well-packed TiO<Subscript>2</Subscript> nanoparticles on multiwall carbon nanotubes using CVD method to fabricate high sensitive gas sensors

Titanium oxide nanoparticles were coated on multiwall carbon nanotubes (MWCNTs) using an atmospheric pressure chemical vapor deposition (CVD) to achieve highly compact nanoparticles of about 5 nm on CNT structure. The CNTs with a diameter of about 50 nm were grown by plasma enhanced CVD. Gas sensitivity of the fabricated structure was investigated and compared with TiO₂/CNT composite-based gas sensors. The effect of the structural interaction between the nanoparticles and the CNT wall on sensing mechanism of the as-prepared gas sensors was investigated. Ultrasensitive gas sensors were obtained by TiO₂/CNT nanostructures with strong interaction between the MWCNT and the TiO₂ nanoparticles. The measurements show high chemical activity and exceptional electrical response of the as-prepared structure being exposed to gases. Scanning and transmission electron microscopy and X-ray diffraction analysis were used to obtain structural information.     

Pd颗粒表面修饰ZnO纳米线阵列的制备及其气敏特性

采用化学气相沉积(CVD)方法在SiO_2/Si衬底生长了ZnO纳米线阵列,纳米线长约为15μm,直径为100~500 nm。通过改变溅射沉积时间(0~150 s),在ZnO纳米线表面包覆了不同厚度的Pd薄膜。在Ar气氛中,经800℃高温退火后,制备出Pd颗粒表面修饰的ZnO纳米线阵列并对其进行了气敏测试。对于乙醇而言,所有传感器最佳工作温度均为280℃。溅射时间的增加(3~10 s)导致ZnO纳米线表面Pd纳米颗粒数量及尺寸增加,传感器响应值由2.0增至3.6。过长的溅射时间(30~150 s)将导致Pd颗粒尺寸急剧增大甚至形成连续膜,传感器响应度显著降低。所有传感器对H2均表现出相对较好的选择性,传感器具有较好的响应-恢复特性和稳定性。最后,探讨了Pd颗粒表面修饰对ZnO纳米线阵列气敏传感器气敏特性的影响机制。     

Elucidating iron doping induced n- to p- characteristics of Strontium titanate based ethanol sensors

A series of pure and iron doped strontium titanate, (SrFe_xTi_1-xO₃; x = 0, 0.1 and 0.2) powders were synthesized, characterized and used to fabricate ethanol sensors for low concentration. X-Ray Diffraction (XRD) technique was used to confirm the single phase formation. Microstructural properties of the powders were investigated using scanning electron microscopy (SEM). Electrical conductivity of all the samples at room temperature (RT) was measured. Sensors were optimized for best responsiveness by varying the operating temperature from 350 °C to 500 °C.The sensor with doping x = 0.2 exhibited best sensing response at 400 °C for ethanol gas. The undoped sensor demonstrated a decrease in resistance on exposure to ethanol gas whereas Fe-doped sensors showed increase in resistance. The doping induced changeover from n to p behavior in the sensing response on doping has been investigated and corroborated with an observed shift in the Fermi level position by X-ray photoelectron spectroscopy (XPS). The disparity in gas sensing response clearly demonstrates inter-connection of multiple influencing factors such as electrical conductivity, morphology, porosity and change in chemical composition on doping. The sensors were exposed to ethanol, nitrogen dioxide, carbon monoxide, butane gases at concentration between 5 ppm and 50 ppm. The sensor exhibited much reduced relative response to all gases other than ethanol which can be utilized for wide range of applications.     

基于银纳米线电极-rGO敏感材料的柔性NO2气体传感器

使用银纳米线作为材料制备柔性叉指电极,用还原氧化石墨烯(reduced graphene oxide, rGO)作为气体敏感材料制备出柔性气体传感器,并研究其对二氧化氮气体的响应特性以及柔韧性能.实验结果表明,制备的以银纳米线作为电极的r GO气体传感器可以实现室温下对浓度为5-50 ppm (1 ppm=10^–6)的NO2气体的检测,对50 ppm的NO2的响应能够达到1.19,传感器的重复性较好,恢复率能够保持在76%以上,传感器的灵敏度是0.00281 ppm^-1,对浓度为5 ppm的NO2气体的响应时间是990 s,恢复时间是1566 s.此外,传感器在0°-45°的弯曲角度下仍表现出优异的电学特性与气体传感性能,所制备的器件具有相对稳定的导电性和较好的弯曲耐受性.     

氧化钨纳米线气敏传感器的制备及其室温NO_2敏感特性

纳米结构的氧化钨有高比表面积和气体吸附能力,在气体传感器领域得到了广泛研究.本文采用磁控溅射金属钨薄膜和两步热氧化工艺在二氧化硅衬底上生长出氧化钨纳米线.通过改变第二步氧化温度,研究退火温度对氧化钨纳米线气敏特性的影响.采用扫描电子显微镜、X射线衍射仪、X射线光电子能谱分析仪和透射射电子显微镜表征材料的微观特性和晶体结构,利用静态配气法测试气敏性能.研究结果表明,经过退火处理后氧化钨纳米线密度略微降低,300℃比400℃退火后的氧化钨结晶性差,对应的表面态含量多,有利于室温气体敏感性.测试NO_2的气敏性能,经过对比得出300℃退火温度下制备的氧化钨纳米线在室温下表现出较很好的气敏响应,对6 ppm(1 ppm=10~(-6))NO_2达到2.5,对检测极限0.5 ppm NO_2响应达1.37.氧化钨纳米线在室温下表现出反常的P型响应,是因为氧化钨纳米线表面被氧气吸附形成反型层,空穴取代电子成为主要载流子所致.     

基于飞秒激光加工的马赫-曾德尔干涉氢气传感器

介绍了一种基于光纤微加工的氢气传感技术方案。利用波长为800nm的飞秒激光脉冲在普通单模光纤上加工马赫-曾德尔(M-Z)干涉腔,并采用磁控溅射方法在加工后的M-Z干涉微腔上溅射钯(Pd)膜,制备了一种新型的光纤氢气传感器。分析了加工工艺对微腔干涉效果的影响,选择合适的加工参数以及加工后对微腔进行后续处理,可使微腔的透射光谱的分辨率得到提高。实验研究了腔长为40μm的M-Z干涉传感器分别镀36nm、110nmPd膜后,对氢气的响应。结果表明,在不同的氢气浓度下,镀Pd膜的M-Z干涉传感器都表现出对氢气的敏感特性,随着氢气浓度的增大,透射光谱会向长波长方向偏移,其中Pd膜厚度为110nm比厚度为36nm的传感器对氢气有更好的灵敏度。     

基于光纤微结构加工和敏感材料物理融合的光纤传感技术

将功能敏感材料与光纤在物理层面进行有机融合,充分发挥光纤传感器在结构集成、材料集成等方面的优势,将有望发展新型的光纤传感器件和系统.本文综述了飞秒激光光纤微加工技术分别在标准的单模光纤和光纤光栅上制备微结构,再结合敏感材料制备技术,实现在物理层面上光纤传感器材料和结构的集成和融合,探索实现新型高性能的光纤传感新技术.     

Low-temperature CO gas sensors based on Au/SnO2 thick film

A study on the low-temperature CO gas sensors based on Au/SnO₂ thick film was reported. Au/SnO₂ powders were prepared by a deposition-precipitation method. Thick films were fabricated from Au/SnO₂ powders. X-ray diffraction (XRD), high-resolution transmission electron microscopy (HRTEM) and X-ray photoelectron spectroscopy (XPS) analyses were carried out for investigation of morphology and crystalline structure. Au/SnO₂ thick film sensors exhibited high sensitivity to CO gas at relatively low operating temperature (83-210 °C). We also reported the effect of the calcination temperature of Au/SnO₂ on the CO gas sensing behavior. The optimal calcination temperature of Au/SnO₂ was 300 °C.     

Functionalized Pd/ZnO Nanowires for Nanosensors

A method for surface doping and functionalization of ZnO nanowires (NWs) with Pd (Pd/ZnO) in a one‐step process is presented. The main advantage of this method is to combine the simultaneous growth, surface doping, and functionalization of NWs by using electrochemical deposition (ECD) at relatively low temperatures (90 °C). Our approach essentially reduces the number of technological steps of nanomaterial synthesis and final nanodevices fabrication with enhanced performances. A series of nanosensor devices is fabricated based on single Pd/ZnO NWs with a radius of about 80 nm using a FIB/SEM system. The influence of Pd nominal composition in Pd/ZnO NW on the H₂ sensing response is studied in detail and a corresponding mechanism is proposed. The results demonstrate an ultra‐high response and selectivity of the synthesized nanosensors to hydrogen gas at room temperature. The optimal concentration of PdCl₂ in the electrolyte to achieve extremely sensitive nanodevices with a gas response (S_H2) ≈ 1.3 × 10⁴ (at 100 ppm H₂ concentration) and relatively high rapidity is 0.75 µM. Theoretical calculations on Pd/ZnO bulk and functionalized surface further validated the experimental hypothesis. Our results demonstrate the importance of noble metal presence on the surface due to doping and functionalization of nanostructures in the fabrication of highly‐sensitive and selective gas nanosensors operating at room temperature with reduced power consumption.     

太阳盲MgZnO光电探测器

利用射频磁控溅射技术在石英衬底上制备了MgZnO合金薄膜,并采用传统湿法刻蚀的方法在薄膜上制备了梳妆叉指Au电极,构成金属-半导体-金属(MSM)结构.在室温下,实现了太阳盲MgZnO光电探测器,器件的探测峰值位于225nm,截止边为230nm.     

Optical path automatic compensation low-coherence interferometric fibre-optic temperature sensor

An interferometric fibre-optic temperature sensing system employing a light emitting diode (LED) as the broadband optical source and a single mode fibre coil which was fabricated in a definite length as the sensor head is described. A reference fibre line transmitting back and forth along the same path as the sensing transmitting fibre is used, so the change caused by the environmental temperature fluctuation of the fibre path can automatically be compensated. The sensitivity of the sensing system can be easily improved by using the long length of the sensing fibre. The experiment results of the sensing gauge length versus the sensitivity are given. Two typical wavelengths (1300 and 1550 nm). LED sources are used, it is shown that the sensitivity of the system between the two wavelengths is different. The experimental curve of the resolution characteristic of the system related to the length of sensing fibre coil is also discussed.     

Effect of 100 MeV O7+ ions irradiation on ethanol sensing response of nanostructures of ZnO and SnO2

Tin dioxide nanoparticles and zinc oxide nanorods were synthesized chemically and thick film gas sensors on alumina substrates were fabricated of these materials. Morphology and crystallite size of synthesized powders were investigated by TEM. The fabricated sensors were irradiated with 100 MeV O⁷⁺ ions at fluences of 1×10¹¹, 1×10¹² and 1×10¹³ ions/cm². The X-ray diffraction analysis of the samples before and after ion bombardment was performed for structural characterization. The sensing response to ethanol before and after irradiation was carried out for each fabricated sensor. Investigation revealed that irradiated SnO₂ based sensor’s response and response time increased significantly. Results show that ZnO based sensor exhibit strong resistance to damage caused by ion irradiation which might be due to defects annihilation.     

Comparison of detectability limits for elemental mapping by EF-TEM and STEM-XEDS

The analytical sensitivity in terms of the signal-to-noise ratio (SNR) was investigated for elemental mapping by a transmission electron microscope equipped with an energy filter (EF-TEM) and a scanning transmission electron microscope with an X-ray energy dispersive spectrometer (STEM-XEDS). To compare the detectability limits of the elemental maps by the two techniques, homogeneous Cu-0.98+/-0.34 wt% Mn and Cu-4.93+/-0.49 wt% Mn thin specimens were used. Elemental maps can be considered as either an image or a spectrum. Therefore, the detectability limits of the elemental maps were characterized by the spectral SNR. To evaluate the detectability limits of the elemental maps with statistical confidence limits such as 1 sigma, 2 sigma and 3 sigma, the SNR values were reviewed from the statistical point of view. In STEM-XEDS mapping, the spectral SNR values improve as the specimen thickness increases since the signal intensity increases. Conversely, the spectral SNR in EF-TEM mapping is maximized at a certain thickness and then reduces as the thickness increases. To compare the two mapping techniques with regard to the analytical sensitivity, a method to estimate the minimum mass fraction (MMF) from measured signal and background intensities was developed. In this experimental approach, the MMF value can be evaluated by selecting the appropriate SNR value corresponding to the statistical confidence limits. In comparing the estimated MMF values from the two mapping approaches, EF-TEM mapping can be more sensitive than STEM-XEDS mapping up to specimen thicknesses <20-30 nm in the 1 sigma confidence limit and < approximately 50 nm in the 3 sigma limits. However, as the specimen thickness increases, the XEDS maps provide better detectability limits in the Cu-Mn dilute alloy specimens.     

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.     

Long-distance fiber Bragg grating sensor system with a high optical signal-to-noise ratio based on a tunable fiber ring laser configuration

A novel tunable fiber ring laser configuration with a combination of bidirectional Raman amplification and dual erbium-doped fiber (EDF) amplification is proposed for realizing high optical signal-to-noise ratio (SNR), long-distance, quasi-distributed fiber Bragg grating (FBG) sensing systems with large capacities and low cost. The hybrid Raman-EDF amplification configuration arranged in the ring laser can enhance the optical SNR of FBG sensor signals significantly owing to the good combination of the high gain of the erbium-doped fiber amplifier (EDFA) and the low noise of the Raman amplification. Such a sensing system can support a large number of FBG sensors because of the use of a tunable fiber Fabry-Perot filter located within the ring laser and spatial division multiplexing for expansion of sensor channels. Experimental results show that an excellent optical SNR of approximately 60 dB has been achieved for a 50 km transmission distance with a low Raman pump power of approximately 170 mW at a wavelength of 1455 nm and a low EDFA pump power of approximately 40 mW at a wavelength of 980 nm, which is the highest optical SNR achieved so far for a 50 km long FBG sensor system, to our knowledge.     

Synthesis of nano-structured materials by laser-ablation and their application to sensors

We describe the synthesis of nano-structured materials of ZnO and Pd by laser ablation and their applications to sensors. The synthesis of ZnO nano-wires was performed by nano-particle assisted deposition (NPAD) where nano-crystals were grown with nano-particles generated by laser-ablating a ZnO sintered target in an Ar background gas. The synthesized ZnO nano-wires were characterized with a scanning electron microscopy and the photoluminescent characteristics were examined under an excitation with the third harmonics of a Nd:YAG laser. The nano-wires with a diameter in the range from 50 to 150 nm and a length of up to 5 μm were taken out of the substrate by laser blow-off technique and/or sonication. It was confirmed that the nano-wires showed the stimulated emission under optical pumping, indicating a high quality of the crystalinity. Pd nano-particles were generated by laser-ablating a Pd plate in pure water. The transmission electron microscope observation revealed that Pd nano-particles with a diameter in the range from 3 nm to several tens of nanometers were produced. Using these nano-structured materials, we successfully fabricated sensors by the dielectrophoresis techniques. In the case of the ultraviolet photosensor, a detection sensitivity of 10 nW/cm² was achieved and in the case of hydrogen sensing, the response time of less than 10 s has been demonstrated with Pd nano-particles.     

Laser-Patterned Carbon-Supported Graphitic Carbon Nitride Quantum Dots for Flexible Nanozyme-Based Fluoride Sensor

Graphitic carbon nitride quantum dots (g-CNQDs)-based colorimetric sensors are typically solution-based and hence incompatible with wearable electronics. Today's competitive technology demands safe and reliable, high-performance sensors suitable for integration with sophisticated electronics—all at a low cost. Herein, a flexible and reusable solid-state fluoride ion sensor manufactured by combining the intriguing surface properties of laser-patterned carbon (LP-C) with the sensitivity of g-CNQDs is reported. LP-C is obtained by direct IR-laser writing onto polyimide films, and g-CNQDs are synthesized via a solvent-free and zero-waste green process. The hybrid of LP-C and g-CNQDs (g-CNQDs/LP-C), mimics the natural enzyme horseradish peroxidase and oxidizes the chromogenic substrate 3,3’,5,5’-tetramethylbenzidine in the presence of H₂O₂ in acidic media. The highly selective and user-friendly nanozyme sensors feature a lower limit of detection of 0.568 ± 0.006  × 10⁻⁶ m (23.8 ± 1.5 µg L⁻¹) with linearity in the range of 0.5 × 10⁻⁶ to 100  × 10⁻⁶ m . A sensing mechanism based on the electronic transitions of g-CNQDs and LP-C, the two variants of nitrogen-containing carbon used in this work, is established. Finally, the device is tested for fluoride ion sensing in natural water samples collected from the Uhl river in Mandi, India.