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.     

钒掺杂W18O49纳米线的室温p型电导与NO2敏感性能

钨氧化物纳米线在高灵敏度低功耗气体传感器中极具应用潜力, 且通过掺杂改性可进一步显著改善其敏感性能. 本文以WCl₆为钨源, NH₄VO₃为掺杂剂, 采用溶剂热法合成了钒掺杂的W₁₈O₄₉纳米线. 利用扫描电镜、透射电镜、X射线衍射、X射线光电子能谱仪表征了纳米线的微结构, 并利用静态气敏性能测试系统评价了掺杂纳米线的NO₂敏感性能. 研究结果表明: 五价钒离子受主掺杂进入氧化钨晶格结构, 抑制了纳米线沿轴向的生长并导致了纳米线束的二次集聚; 室温下, 钒掺杂W₁₈O₄₉纳米线接触NO₂气体后表现出反常的p型响应特性; 随工作温度逐渐升高至约110 ℃时, 发生从p型到n型的电导特性转变; 该掺杂纳米线气敏元件对浓度低至80 ppb (1 ppb=10^-9) 的NO₂气体具有明显的室温敏感响应和良好的响应稳定性. 分析并探讨了钒掺杂W₁₈O₄₉纳米线的高室温敏感特性及其p-n电导转型机理, 认为钒掺杂W₁₈O₄₉纳米线在室温下的良好敏感响应及反常p型导电性与掺杂纳米线表面高密度非稳表面态诱导的低温气体强吸附有关. 关键词： 氧化钨 纳米线 气体传感器 室温灵敏度     

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     

基于4，8-二氢二呋咱[3，}4-b，e]吡嗪高能材料的设计与筛选

为了寻找高能量密度的材料,本文设计了一系列基于4,8-二氢二呋咱[3,4-b,e]吡嗪的含能材料. 利用密度泛函理论研究了它们结构与性质之间的关系. 结果表明,这些设计化合物的性质受到含能基团和杂环取代基的影响. -N₃含能基团是提高设计化合物生成热的最有效取代官能团,而四唑环/-C(NO₂)₃基团对炸药的爆轰性能有较大贡献. 键解离能分析表明,引入-NHNH₂,-NHNO₂,-CH(NO₂)₃和-C(NO₂)₃基团会显著降低键解离能. 由于化合物A8,B8,C8,D8,E8和F8具有良好的爆轰性能和热稳定性,最终被筛选为潜在的高能密度材料. 此外,还计算了这些筛选化合物的电子结构.     

径向生长的具有分级结构的四氧化三钴微晶及其在气体传感上的应用

通过在水热合成后追加退火处理,制备了径向生长的具有分级结构的树枝状三维Co₃O₄晶体,并用X射线衍射仪、扫描电子显微镜和透射电子显微镜对其结构和形貌进行了表征. 在110 oC对其气体探测性能的研究表明这种Co₃O₄分级结构对氨气有较高的探测灵敏度和响应速度(10 s),性能稳定并具有可重复性. 同时,还在较低的探测温度下对酒精、丙酮和苯进行了气敏探测.     

Sb2Te3 纳米结构的制备与表征

以室温热电性能优异的传统热电材料Sb₂Te₃为研究对象,利用化学气相沉积法制备Sb₂Te₃单晶纳米结构,并研究其生长机理.实验结果表明,不加催化剂时Sb₂Te₃易生长成六方纳米盘,在金催化剂条件下定向生长成纳米线.Sb₂Te₃的形貌与其晶体结构和生长机理有关.Sb₂Te₃为三角结构,Sb和     

FeCo二元合金纳米线阵列的磁化反转

利用交流电化学沉积方法在氧化铝模板中制备了一维结构的Fe_xCo_1-x(0 ≤ x ≤ 0.51)二元合金纳米线阵列.X射线衍射结果显示,单质Co纳米线为(100)择优取向的hcp结构,FeCo合金纳米线则呈现(110)择优取向的bcc结构,而且衍射峰随纳米线中Fe含量的增加向低角度偏移.室温磁性测量结果显示, FeCo合金纳米线具有较好的磁特性.与Co纳米线相比,Fe的引入改善了Co纳米线的磁性能,使其呈现出较大的矫顽力和较高的矩形比.采用一致转动模型和对称扇形机理的球链模型分别计算了FeCo合金纳米线的矫顽力, 发现其磁化反转机理与对称扇形机理的球链模型相符合.     

利用氧化辅助气固法生长高磁性的α-Fe2O3和Fe3O4纳米线

探讨生长α-Fe₂O₃和Fe₃O₄纳米线的一个可控制的合成过程. 在研究中发现,高磁性的α-Fe₂O₃纳米线已经成功地利用氧化辅助气固法结晶生成于Fe_0.5Ni_0.5合金基板上;若基板事先浸泡于草酸溶液中,随草酸浓度的增加,所生长的纳米线晶相会逐转变为Fe₃O₄,当草酸浓度达到0.75 mol/L时,所生长的纳米线几乎全部转变成Fe₃O₄晶相. 此外,实验结果也显示所生长的纳米线长度及直径会随着气固过程中的温度上升而增加,生长密度则会随着气固过程中的流量加大而上升. 此过程所提出的合成程序可在2 h內完成.     

微流控技术制备ZnO纳米线阵列及其气敏特性

利用微流控技术在微通道中制备了Zn O纳米线阵列,通过X射线衍射和扫描电子显微镜分别对纳米线的物相和表面形貌进行了表征.结果发现,合成的Zn O纳米线具有良好的c轴择优取向性和结晶度.同时,对Zn O纳米线阵列在丙酮、甲醇和乙醇气体中的气敏特性进行了研究,测试结果表明:在最佳工作温度(475?C)下,纳米线阵列对200 ppm(1 ppm=10-6)丙酮气体的最大灵敏度可达8.26,响应恢复时间分别为9和5 s;通过与传统水热法制备的Zn O纳米线的气敏性能相比较发现,基于微流控技术制备的纳米线阵列具有更高的灵敏度和更快的响应恢复速度.最后,从材料表面氧气分子得失电子的角度对Zn O纳米线气敏机理进行了讨论.     

硅纳米线/氧化钒纳米棒复合材料的制备与气敏性能研究

采用纳米球光刻和金属辅助刻蚀法以p型单晶硅片制备了硅纳米线阵列, 并以此作为基底, 通过溅射不同时长的金属钒薄膜并进行热退火氧化处理, 制备出硅纳米线/氧化钒纳米棒复合材料. 采用扫描电子显微镜和X射线衍射仪表征了该复合材料的微观特性, 结果表明该结构增大了材料的比表面积, 有利于气体传感, 并且镀膜时间对后续生长的氧化钒纳米棒形貌有明显影响. 采用静态配气法在室温下测试了该复合材料对NO₂的气敏性能, 气敏测试结果表明沉积钒膜的时间对复合材料的气敏性能影响较大. 当选择合适的镀膜时间时, 适量氧化钒纳米棒增加了材料表面积并形成大量pn结结构, 相比纯硅纳米线对NO₂气体的灵敏度有明显提升, 且在室温下表现出优良的选择性. 同时, 对气敏机理做了定性解释, 认为硅纳米线与氧化钒纳米棒之间形成的pn结及能带结构在接触NO₂ 时的动态变化是其气敏响应提升的主要机制.     

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.     

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.     

Preparation and characterisation of ZnFe2O4/ZnO polymer nanocomposite sensors for the detection of alcohol vapours

During the last 10 years, a large interest has developed in the preparation of nanocomposite structures by embedding inorganic nanoparticles into polymeric materials. These materials combine the properties of the inorganic fillers with the processability and flexibility of polymers. The versatility of polymer nanocomposite systems is of special interest to the gas sensor industry where arrays of polymer/carbon black composites have been used to identify gases and odours. These polymer gas sensors provide selectivity based on their chemical structures and operate at room temperature, which provide advantages over thick-film metal oxide gas sensors. ZnFe₂O₄ and ZnO have excellent stability, high sensitivity, low fabrication complexity and moderate operating temperatures, which are ideal properties for a gas sensing material. In this work, the development of a thick-film ZnFe₂O₄/ZnO sensor, which operates at room temperature and a drop-coated conducting polymer composite sensor containing 30 w/w% ZnFe₂O₄/ZnO nanoparticles is discussed. The sensors were tested in a fully automated test rig and showed promising results for the detection of alcohol vapours.     

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.     

Drastic change in shape of tetragonal TeO2 nanowires and their application to transparent chemical gas sensors

We have synthesized one-dimensional structures of tellurium dioxide (TeO₂) by heating of tellurium powders. Their morphology was drastically changed as the growth temperature increased in the range of 400-500 °C, in which high-temperature process facilitated the thickening of the stem nanowires, as well as the growth of secondary branches on the stems. The obtained TeO₂ products were crystalline with tetragonal structure. The TeO₂ nanowire film exhibited a high transmission rate of about 73%. We have investigated the NO₂ sensing properties of the as-fabricated TeO₂ nanowires, in which a linear relationship between sensitivity and the NO₂ gas concentration was observed. Thus, the TeO₂ nanowires demonstrated their potential application to transparent chemical sensors.     

Nonlinear optical and optical limiting properties of individual single-walled carbon nanotubes

A large number of individual single-walled carbon nanotubes (SWNTs) were obtained by dilution of nanotube dispersions in N-methyl-2-pyrrolidone (NMP). Up to 70% individual SWNTs are contained in the NMP dispersions with concentrations of less than 4.0×10^-3 mg/mL. The nonlinear optical and optical limiting properties of SWNT dispersions were studied by using the Z-scan technique at 532 nm. As the concentration of SWNTs is increased, the nonlinear extinction (NLE) and optical limiting effects improve significantly, while the limiting thresholds decrease gradually. The individual SWNTs show similar NLE effect to zinc phthalocyanine nanoparticles, while also exhibiting larger NLE coefficients than Mo₆S_4.5I_4.5 nanowires.     

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.     

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.