Humidity-resistant ammonia sensor based on PTFE/ZnO/Ti3C2Tx composite films
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摘要: 开发基于半导体功能材料的抗湿性室温气体传感器一直都是气体传感器领域的研究热点和难点。本文从金属氧化物半导体的高灵敏度和稳定性、MXene (Ti3C2Tx)的室温气敏性以及聚四氟乙烯(PTFE)的疏水性出发，以MXene薄膜为基体，采用磁控溅射法分别将ZnO和PTFE沉积到Ti3C2Tx表面，制备了PTFE/ZnO/MXene复合薄膜，同时构筑了基于复合薄膜的气体传感器。通过SEM、TEM和XPS对复合薄膜进行了表征，并对气体传感器的气敏性能和抗湿性能进行了研究。研究结果表明：基于PTFE/ZnO/Ti3C2Tx复合薄膜的气体传感器在室温下对氨气具有良好的选择性、较高的灵敏度和优异的循环稳定性。随着PTFE薄膜厚度的增加，基于复合薄膜的气体传感器的抗湿性能逐渐增加，但灵敏度有所下降。
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关键词:
- PTFE/ZnO/MXene复合薄膜 /
- 抗湿性 /
- 磁控溅射 /
- 气体传感器 /
- 氨气
Abstract: The development of moisture-resistant room-temperature gas sensors based on semiconductor functional materials has always been a hot and difficult research topic in the field of gas sensors. Considering the high sensitivity and stability of metal oxide semiconductor, the room-temperature gas-sensing behaviors of MXene (Ti3C2Tx) and the hydrophobicity of polytetrafluoroethylene (PTFE), the PTFE/ZnO/MXene composite films were prepared by depositing the PTFE and ZnO layers orderly onto the MXene film surface via a magnetron sputtering method, followed by the construction of the gas sensors based on the composite films. The PTFE/ZnO/MXene composite films were characterized by SEM, TEM and XPS, and the gas-sensing and humidity-resistant properties of the composite films-based gas sensors were investigated. Results show that the PTFE/ZnO/Ti3C2Tx composite films-based gas sensors exhibite good selectivity, high sensitivity, and excellent reproducibility towards ammonia at room temperature. With the increase of the thickness of the PTFE layers, the humidity resistance of the composite films-based gas sensors gradually increases, but at the cost of sensitivity.-
Key words:
- PTFE/ZnO/MXene composite films /
- moisture resistance /
- magnetron sputtering /
- gas sensor /
- ammonia
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图 1 薄膜的SEM图像以及EDS图像：(a) Ti3C2Tx薄膜；((b), (d)) ZnO/Ti3C2Tx薄膜；((c), (e)) PTFE/ZnO/Ti3C2Tx-4 薄膜
Figure 1. SEM images as well as EDS images of thin films: (a) Ti3C2Tx thin film; ((b), (d)) ZnO/Ti3C2Tx thin film; ((c), (e)) PTFE/ZnO/Ti3C2Tx-4 thin film
图 2 长期稳定性测试后薄膜的SEM图像以及EDS图像：((a), (c)) ZnO/Ti3C2Tx薄膜；((b), (d)) PTFE/ZnO/Ti3C2Tx-4薄膜
Figure 2. SEM images as well as EDS images of the films after long-term stability tests: ((a), (c)) ZnO/Ti3C2Tx film; ((b), (d)) PTFE/ZnO/Ti3C2Tx-4 film
图 3 薄膜的XPS图谱：(a) 全谱图；(b) Ti2p；(c) C1s；(d) O1s；(e) F1s
Figure 3. XPS spectra of thin films: (a) Full spectra; (b) Ti2p; (c) C1s; (d) O1s; (e) F1s
图 4 长期稳定性测试后薄膜的XPS图谱：(a) 全谱图；(b) O1s
Figure 4. XPS spectra of the films after long-term stability testing: (a) Full spectra; (b) O1s
图 5 不同传感器的气敏响应测试：(a) 对100×10−6氨气的响应图；(b) 对100×10−6氨气的响应/恢复时间；(c) 对不同挥发性有机化合物的响应雷达图(100×10−6氨气、500×10−6异丙醇、乙醇、丙酮和甲醛)；(d) 对5×10−6~500×10−6氨气的动态响应曲线；(e) 对不同浓度氨气的响应保持率(传感器均在室温下相对湿度为 30%的条件下监测)
Figure 5. Air sensitive response testing of different sensors: (a) Response to 100×10−6 ammonia; (b) Response/recovery time to 100×10−6 ammonia; (c) Radar plots of the response to different volatile organic compounds (100×10−6 ammonia, 500×10−6 isopropanol, ethanol, acetone, and formaldehyde); (d) Dynamic response curves of the response to ammonia from 5×10−6-500×10−6; (e) Response retention curves of different concentrations of ammonia (All sensors were tested at room temperature with 30% relative humidity)
图 6 传感器的稳定性测试：(a) PTZ-4传感器对100×10−6氨气的循环响应图；(b) PTZ-4传感器对100×10−6氨气循环响应的灵敏度点线图；(c) TZ传感器25天内对100×10−6氨气响应图；(d) TZ传感器和PTZ-4传感器25天内对100×10−6氨气响应的灵敏度点线图；(e) PTZ-4传感器25天内对100×10−6氨气响应图；(f) 25天的初始电阻变化率图(Ran是传感器第n天的初始电阻)
Figure 6. Stability testing of the sensors: (a) Plot of the cyclic response of the PTZ-4 sensor to 100×10−6 ammonia; (b) Dot line plot of the sensitivity of the PTZ-4 sensor to the cyclic response of 100×10−6 ammonia; (c) Plot of the response of the TZ sensor to 100×10−6 ammonia over 25 days; (d) Sensitivity dot line plot of the response of both the TZ and PTZ-4 sensors to 100×10−6 ammonia over 25 days; (e) Plot of PTZ-4 sensor response to 100×10−6 ammonia over 25 days; (f) Plot of initial resistance change rate over 25 days (Ran is the initial resistance of the sensor on n days)
图 7 传感器在室温下对100×10−6氨气在不同相对湿度(RH)条件下响应-恢复曲线以及对应的水接触角(WCA)：((a), (b)) TZ；((c), (d)) PTZ-3；((e), (f)) PTZ-4；((g), (h)) PTZ-5；((i), (j)) PTZ-8；(k) 传感器在30%~90%相对湿度范围内的变化指数(CV)值
Figure 7. Sensor response-recovery curves for 100×10−6 ammonia at room temperature under different relative humidity (RH) conditions and corresponding water contact angle (WCA): ((a), (b)) TZ; ((c), (d)) PTZ-3; ((e), (f)) PTZ-4; ((g), (h)) PTZ-5; ((i), (j)) PTZ-8; (k) Coeffficient of variation (CV) of the sensor in the range of 30%-90% RH
图 8 ZnO/Ti3C2Tx异质结构的能带状态示意图
Figure 8. Schematic energy band states of the ZnO/Ti3C2Tx heterostructure
EVAC—Vacuum energy level; EC—Conductive belts; EF—Fermi level; EV—Price band; EΦ—Work functions; Eg—Banned; △ΦB—Schottky barrier
图 9 ZnO/Ti3C2Tx 异质结构的传感机制示意图
Figure 9. Schematics of sensing mechanism of ZnO/Ti3C2Tx heterostructure
表 1 传感器命名
Table 1. Sensor naming
Sample PTFE sputtering time/min PZT-3 3 PZT-4 4 PZT-5 5 PZT-8 8 Notes: PZT—PTFE/ZnO/Ti3C2Tx; PTFE—Polytetrafluoroethylene. 
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