GAS SENSITIVE SEMICONDUCTOR NANOMATERIALS FOR CREATION OF HYDROGEN SENSORS

I. Matushko, L. Oleksenko, N. Maksymovych, Galina Skolyar, O. Roik, G. Fedorenko, L. Lutsenko, Oleksandr Ripko
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Abstract

Co-precipitaion method and sol-gel technique were used to prepare semiconductor microcrystalline and nanosized SnO2/Sb2O5 and Со/SnO2/Sb2O5 (0.15 wt.% Sb) materials aimed to create high sensitive hydrogen sensors. Morphology and phase composition of the obtained samples were studied by SEM, TEM and XRD methods. It was found that microcrystalline SnO2/Sb2O5 material with particle size of 1–30 μm was obtained by a co-precipitation method and nanosized SnO2/Sb2O5 material with particle size of 5–25 μm (an average size – 12 nm) was obtained by a zol-gel method. Only cassiterite phase was detected for both microcrystalline and nanosized materials. Sensitivity measurements of the sensors were carried out with using of air-hydrogen mixtures in the concentration range of 40 – 1145 ppm Н2, and dynamic characteristics (response time and relax time) were evaluated for 40 ppm Н2 at different heater power consumptions – 0.25 and 0.35 W. To increase sensitivities of the sensors, cobalt oxide, a known catalyst for hydrogen oxidation, was added to the resulting SnO2/Sb2O5 materials. It was shown that the sensors obtained by a zol-gel method demonstrate more significant sensitivity to hydrogen concentration in comparison with the sensors obtained by a co-precipitation method. It is probably associated with a higher surface area of the nanomaterial that agrees with its smaller particles as compared with the particles of the microcrystalline material. The Co-containing sensors based on the nanosized SnO2/Sb2O5 material are established to reveal higher sensitivity to Н2 than microcrystalline Co/SnO2/Sb2O5 sensors. The Co-containing sensors based on the nanosized SnO2/Sb2O5 material were found to have better dynamic characteristics than microcrystalline Co/SnO2/Sb2O5 sensors. The sensitivities increase and the response and recovery time decrease were found for both sensor materials at increasing of the sensors heater power consumption. The obtained results can be explained with different degree of energy surface heterogeneity of the used materials. The sensor response time is determined by the time of dynamic equilibrium establishment of the hydrogen oxidation reaction on the sensor surface and the recovery time is determined by the time of desorption of the H2 oxidation reaction products (H2O) from the sensor surface. Because of the processes, the sensor with a gas sensitive layer based on the nanosized material possessing with more homogeneous structure of its surface (according to the obtained TEM data) demonstrates improved gas sensitive properties in comparison with the sensor based on the microcrystalline material. The obtained results concerning the sensitivities to H2 and the dynamic parameters of the created sensors point to possibility of effective usage of the sensors based on the nanomaterial to detect H2 in air in the practice.
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用于制造氢传感器的气敏半导体纳米材料
采用共沉淀法和溶胶-凝胶技术制备了半导体微晶和纳米级SnO2/Sb2O5和Со/SnO2/Sb2O5 (0.15 wt.% Sb)材料,旨在制造高灵敏度的氢传感器。采用SEM、TEM和XRD等方法研究了样品的形貌和相组成。结果表明,共沉淀法可获得粒径为1 ~ 30 μm的SnO2/Sb2O5微晶材料,zol-gel法可获得粒径为5 ~ 25 μm(平均粒径为- 12 nm)的SnO2/Sb2O5纳米材料。在微晶和纳米材料中只检测到锡石相。在40 - 1145 ppm Н2的空气-氢混合物浓度范围内对传感器的灵敏度进行了测量,并在不同的加热器功率消耗(0.25和0.35 W)下,对40 ppm Н2的动态特性(响应时间和放松时间)进行了评估。为了提高传感器的灵敏度,将已知的氢氧化催化剂氧化钴添加到所得的SnO2/Sb2O5材料中。结果表明,与共沉淀法相比,zol-gel法获得的传感器对氢浓度的灵敏度更高。这可能与纳米材料的高表面积有关,与微晶材料的颗粒相比,纳米材料的颗粒更小。基于纳米SnO2/Sb2O5材料的含Co传感器对Н2的灵敏度高于微晶Co/SnO2/Sb2O5传感器。基于纳米SnO2/Sb2O5材料的含Co传感器比微晶Co/SnO2/Sb2O5传感器具有更好的动态特性。随着传感器加热器功耗的增加,两种传感器材料的灵敏度均增加,响应时间和恢复时间均减少。所得结果可以用所用材料不同程度的能量表面非均质性来解释。传感器响应时间由传感器表面氢氧化反应建立动态平衡的时间决定,恢复时间由传感器表面氢氧化反应产物(H2O)解吸的时间决定。由于这些工艺,基于纳米材料的气敏层传感器具有更均匀的表面结构(根据获得的TEM数据),与基于微晶材料的传感器相比,具有更好的气敏性能。所获得的传感器对氢气的灵敏度和动态参数的结果表明,基于纳米材料的传感器在实际中有效应用于空气中氢气的检测是可能的。
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