Mesoporous nanoparticle TiO2 thin films for conductometric gas sensing on microhotplate platforms

Mesoporous TiO₂ nanoparticle thin films were prepared on MEMS microhotplate (μHP) platforms and evaluated as high-sensitivity conductometric gas sensor materials. The nanoparticle films were deposited onto selected microhotplates in a multi-element array via microcapillary pipette and were sintered using the microhotplate. The films were characterized by optical and scanning electron microscopies and by conductometric measurements. The thin films were evaluated as conductometric gas sensors based on the critical performance elements of sensitivity, stability, speed and selectivity. The nanoparticle films were compared with compact TiO₂ films deposited via chemical vapor deposition (CVD) and the nanoparticle films were found to demonstrate higher sensitivity to target analytes. The nanoparticle films were also stable with regard to both baseline conductance and signal response over 60 h of continuous operation at high temperatures (up to 475 °C). Sensor response times were evaluated and the TiO₂ nanoparticle films showed fast responses to the presence of analyte (≈5 s) and a response-time dependence on the analyte concentration. Control of the sensor operating temperature, an inherent benefit of the microhotplate platform, was employed to demonstrate the selectivity of the nanoparticle films.     

退火处理对Ti-WO_3薄膜的结构和气敏特性的影响

用X射线衍射和透射电镜表征了直流磁控溅射法制得的Ti-WO3薄膜的晶型、晶格常数、粒径等。研究了退火对Ti-WO3薄膜气敏性质和微结构的影响,找出了最佳退火温度和工作温度;并对机理进行了分析。结果表明:450℃退火的薄膜的气敏效应很好,最佳工作温度在150℃左右;     

利用原子力显微镜观测气敏薄膜的平整度

介绍原子力显微镜功能、原理和结构,用于检测原子之间的接触来呈现样品的表面形貌特性,如粗糙度、起伏不平整度等,提供三维表面图像。常用的是激光反射检测系统,由探针、激光发生器和光检测器组成。探针是由悬臂和悬臂末端的针尖组成,悬臂是由Si或Si3N4经光刻技术用MEMS技术加工而成。当在样品表面扫描的探针引起悬臂梁弯曲时,产生应力。再由压电陶瓷能将十几分之一纳米到几微米的位移而导致的应力信号转换成1mV~1000V的电信号,以代表样品表面的不平整度。同时简单介绍了利用原子力显微镜观察不同退火温度对制备的气敏传感器薄膜表面晶粒度的影响,以及不同腐蚀液抛光硅片的效果。     

Comparative gas sensing in copper porphyrin and copper phthalocyanine spin-coating films

Spin-coating films of tetra-(tert-butyl)-5,10,15,20-tetraazaporphyrin copper (CuTAP(t-Bu)₄) and tetra-(tert-butyl) phthalocyanine copper (CuPc(t-Bu)₄) was obtained and characterized by absorption spectra and atomic force microscopy. The gas sensing behaviors of the films were investigated with respect to NH₃ and NO₂ at room temperature. In addition, the interactions between complexes and gas analytes were also discussed. It was found that the devices exhibited better response and slow response-recovery times with increase of interactions between the complexes and analytes related with conjugated ability of complexes. This suggests that the response may imparted by use of strong interactions between the complexes and the analyte of interest at the expense of reversibility.     

纳米WO_3粉体的制备及其气敏性能研究

采用溶胶—凝胶法分别用草酸和苯甲酸为凝胶剂制得纳米WO3粉体。通过XRD,TEM等手段对粉体的粒度、晶体结构、形貌等进行了表征,探讨了煅烧温度、工作温度、气体体积分数及不同酸作凝胶剂对气敏性能的影响。结果表明:2种情况所得元件均对NO2有1000以上的灵敏度和较高的选择性,且苯甲酸做凝胶剂有较低的工作温度(125℃)和很快的响应时间(1 s),用草酸做凝胶剂时的恢复时间只有7 s。纳米WO3厚膜NO2传感器是一种实用前景良好的传感器。     

ZnSnO3气敏薄膜的制备和性能

利用共沉淀法制备了ZnSnO3粉体,通过直流溅射制备了气敏薄膜.研究了老化温度、薄膜的组成对气体的灵敏度影响.实验结果表明:600℃老化后,气敏膜薄膜的主要成分是ZnSnO3,在450℃时,该薄膜对乙醇灵敏度约为650,有望开发成酒敏元件.     

CeO2掺杂对ZnO薄膜气敏特性的影响

ZnO薄膜进行CeO2掺杂,研究掺杂含量和热氧化对薄膜结构、表面、晶粒尺寸及气敏特性的影响.结果显示,用热蒸发制备的高纯Zn膜经500℃热氧化,获得c轴取向ZnO多晶薄膜.掺CeO2可抑制晶粒生长使颗粒细化平均粒径减小,同时改善了ZnO薄膜的体相化学计量比,Zn与O的比例从未掺杂时1∶1.28降到1∶1.191.XPS...     

碳纳米管掺杂WO_3气敏元件敏感特性的研究

研究以碳纳米管(CNT)为掺杂剂制备的CNT-WO3旁热式气敏元件。采用球磨、超声分散的方法对碳纳米管进行分散处理,溶胶—凝胶方法制备WO3微粉,用SEM观察了WO3气敏材料的显微结构,测试了元件对丙酮的气敏性能。结果表明:碳纳米管存在于平均粒径为30~50 nm的WO3晶粒间,从而增加了材料的气孔率。碳纳米管掺杂元件对丙酮的灵敏度远高于纯WO3元件,质量分数为0.4%的掺杂量对丙酮有最高灵敏度,具有能检测低体积分数丙酮气体、选择性好的优点,特别是掺杂碳纳米管明显提高了WO3元件的响应速度。     

纳米WO_3薄膜的光学性质及氢敏特性研究

采用磁控直流溅射法制备出纳米WO3薄膜,在N2气中进行退火处理。采用分光光度计、XRD等对退火前后的WO3薄膜进行了光学特性的分析。研究表明:在623 K进行退火处理的薄膜均匀、致密,呈现出较好的结晶态。采用光源激发对纯WO3薄膜在不同温度条件下的氢敏特性进行了研究,实验显示:WO3薄膜对H2的敏感性与温度有关,在348 K温度条件下,WO3薄膜的氢敏效应最好。     

Orientation and thickness dependence of electrical and gas sensing properties in heteroepitaxial indium tin oxide films

Heteroepitaxial indium tin oxide (ITO) films were grown on three differently oriented yttria-stabilized zirconia (YSZ) substrates ((1 0 0), (1 1 0), (1 1 1)) by rf magnetron sputtering, and their structural characteristics and electrical and gas sensing properties were investigated. The initially formed ITO exhibited an island structure on the very thin layer and became a continuous film after the prolonged deposition. The heteroepitaxial relationships between ITO films and YSZ substrates were confirmed by X-ray diffraction, pole figure, and high resolution transmission electron microscopy (HRTEM). The chemical composition, determined by X-ray photoelectron spectroscopy (XPS), was slightly different at early stage depending on the substrate orientation, but it became similar after the longer deposition. Hall measurements indicated that the electrical resistivity of ITO films decreased with increasing the deposition time (or film thickness) irrespective of the film orientation. The ITO film deposited on (1 1 0) YSZ for 10 s showed the highest electrical resistivity. The gas sensor fabricated from the ITO film on (1 1 0) YSZ deposited for 10 s showed the highest NO₂ gas response at relatively low temperature (100 °C), which was attributed to the higher Sn concentration and higher surface roughness of that film.     

八异戊氧基酞菁铅旋涂膜对NO2的气敏性研究

为了筛选性能优良的酞菁类气敏性材料,设计合成了可溶性的八异戊氧基酞菁铅.利用旋涂技术制备了较理想的八异戊氧基酞菁铅旋涂膜,研究了八异戊氧基酞菁铅旋涂膜对NO2气体的敏感特性.研究表明,室温下八异戊氧基酞菁铅旋涂膜对NO2表现出良好的敏感性,响应浓度为5 mg·m-3,响应恢复较快,对浓度为40 mg·m-3的响应时间为30 s,恢复时间为1.5 min,并且该旋涂膜对NO2气体表现出较理想的可逆性、稳定性和选择性.     

WO_3气敏薄膜的膜厚对气体响应时间的影响

用简单的模型分析了薄膜气体传感器敏感材料的膜厚对气体响应时间的影响,该模型适用于分析WO3薄膜气体传感器的敏感特性。薄膜气体传感器的敏感特性依赖于气体原子在薄膜内的扩散和与气敏材料的响应;而气体原子在薄膜内的扩散是由薄膜厚度决定的。经过推导得出理论上WO3薄膜对NH3的敏感特性,并将其与实验所得的数据进行比较。最后,给出了WO3薄膜气体传感器的气敏特性与气体在其膜内扩散和膜厚的关系。     

铈掺杂WO_3纳米材料气敏特性研究

以金属W粉为原料采用溶胶—凝胶法制得纳米级WO3粉体,探讨了不同CeO2添加量对气敏特性的影响。CeO2掺杂WO3材料对挥发性有机化合物(VOCs)气体灵敏度有显著提高,而器件的工作温度有所降低。FE—SEM测试结果说明:CeO2掺杂对晶界的移动形成某种"钉扎"效应,使晶粒减小,比表面积增大。复阻抗谱分析认为,Ce4+主要存在于晶界,使晶界电阻增大,晶界电容减小,提高了WO3材料的气敏特性。     

Examination of Au/SnO2 core-shell architecture nanoparticle for low temperature gas sensing applications

Au/SnO₂ core-shell structure nanoparticles (NPs) were synthesized using two methods, microwave and conventional precipitation. In both cases, the size of the Au core was 12-18 nm and the thickness of the SnO₂ shell was 8-12 nm. The particle size of SnO₂ synthesized using the microwave and precipitation method was 3-5 nm and 1-2 nm, respectively. Upon heating to 400-600 °C, both particles maintained their core-shell morphology but the smaller SnO₂ particles prepared using the precipitation method were more sintered. The resistance changes in films of these particles were measured as a function of CO concentration. The Au/SnO₂ particles prepared using the microwave method showed higher sensor response than those prepared using the precipitation method, even providing a significant signal at testing temperatures approaching ambient conditions, thereby affording a new class of material for gas sensing. Both sets of core-shell particles showed higher sensor response than the SnO₂ nanoparticles. The role of the Au core as a catalyst in improving the adsorption and oxidation of CO gas is important for improving the low temperature response. In addition, the maintenance of the size of SnO₂ in the microwave method during sintering contributed to the higher response towards CO sensing.     

Zn2+掺杂WO3基气敏材料的制备及气敏性能研究

通过加热分解钨酸制备的WO3与Zn(NO3)2溶液超声分散,制备出了掺杂Zn2 的WO3基气敏材料。研究了Zn2 掺杂对WO3气敏材料性能的影响。结果发现,Zn2 掺杂WO3基传感器对H2S有较好的气敏性能,在常温下对极低浓度(5×10-6)H2S也有很高的灵敏度(56),适量掺杂可以提高其灵敏度,Zn2 掺杂n_Zn~(2 )/n_W=2%的WO3基传感器的灵敏度最大,对50×10-6H2S在200℃灵敏度可达1800。通过X-射线衍射仪(XRD),比表面测定仪(BET)对材料进行了表征,比表面积范围介于2.5～3.5m2/g之间。结合有关理论,对元件气敏现象及机理进行了解释。     

纳米LaFeO3的制备及H2S气敏性能研究

以无机物K3[Fe(CN)6]和La(NO3)3·nH2O为原料,用热分解配合物前驱体法制备了LaFeO3纳米粉体.用X-射线粉末衍射仪(XRD)和透射电镜(TEM)对产物的物相、形貌进行了表征.本工作还以沉淀法相同温度条件下煅烧出的LaFeO3作了对比.结果显示:热分解法在煅烧温度为700℃即可生成纳米晶LaFeO3,TEM显示产物为均匀的椭球形颗粒,充分表明该方法制备的材料具有良好分散性,且纯度较高.将合成材料制备成旁热式气敏元件,气敏性能测试结果表明:合成材料对H2S具有高的灵敏度和选择性,在192℃工作时,对35μL/L H2S气体的灵敏度可达72倍.     

TiO_2/V_2O_5双层薄膜的TMA气敏特性研究

报道了以TiCl4 和V2 O5为源 ,采用等离子增强化学气相沉积 (PECVD)和溶胶 -凝胶 (sol-gel)技术制备了TiO2 /V2 O5双层薄膜 ,将该薄膜沉积在带有金梳状电极的陶瓷管和硅片上 ,进行了X射线衍射(XRD)分析 ,并且测量其对三甲基胺 (TMA)的气敏特性。结果发现该双层薄膜对TMA具有高灵敏度、良好的选择特性和快速的响应恢复特性。     

Phthalocyanines as sensitive coatings for QCM sensors: Comparison of gas and liquid sensing properties

The quartz crystal microbalance (QCM) was used to investigate the liquid sensing properties of a set of phthalocyanines (Pcs) which were systematically varied by attaching the substituent 2,2,3,3-tetrafluoropropyloxy to different positions and by introducing a central metal ion (i.e. Ni²⁺, Zn²⁺, and Cu²⁺). The responses to low concentrations of organic compounds such as hydrocarbons and chlorocarbons dissolved in water were recorded. The materials were very sensitive to the tested compounds with detection limits in the lower parts-per-million range and they exhibited a good sensing performance as the sensors have been working fully reversibly and reliably over long periods of time. Besides, the influence of substitution pattern and choice of central metal ion on the liquid sensing properties of Pcs were studied for the first time. The results show that the responses differ notably from each other depending on the modifications made to the Pc. Finally, it is demonstrated that the gas and liquid sensing responses of the materials are highly correlated and can be linked to each other with the help of a basic physical model.     

WO3掺杂对NiO基纳米材料VOCs气体气敏性能的影响

用均匀共沉淀法制备纳米NiO材料,研究不同WO3添加量对材料气敏性能的影响.WO3的掺杂使NiO气敏材料对挥发性有机物(VOCs)气体的灵敏度有显著的提高,且通过XRD图谱分析,WO3的添加抑制了NiO晶粒生长,增大了材料的比表面积,改善了NiO材料的气敏性能.     

Pt/Pd对WO_3燃气敏感元件的影响

在WO3粉体材料中加入Pt,PtO2,Pd,PdCl2,以恒温600℃烧结1h制成旁热式厚膜可燃性气敏元件。采用静态电压测量法,研究了元件的加热电压与元件灵敏度的关系。实验结果表明:WO3元件掺入质量分数为0.5%的Pt/Pd,在加热功率为600 mW时,能提高元件的灵敏度2~10倍。