CsPbBr3 quantum dots passivated by acetylacetone indium and their room-temperature methanol gas sensitivity
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摘要: 甲醇气体对人体具有毒性，会损害人的神经系统和血液循环系统，开发能够检测甲醇的器件有十分重要的意义。传感器法检测甲醇具有成本低、灵敏度高且可实时监测的优点，但目前主流的甲醇气体传感器主要以金属氧化物为主，存在工作温度高的缺点。本文通过简单的溶液合成法合成了钙钛矿量子点CsPbBr3，并采用乙酰丙酮铟配体(In(Acac)3)来对其表面缺陷进行钝化，获得了室温对甲醇具有较好气敏性的材料。在室温下对体积分数为80×10–6甲醇气体相应灵敏度为0.25，响应恢复时间为11.0 s/17.0 s，在紫外光照射下传感器的气体响应性能进一步提高。传感器具有良好的可再现性和稳定性，传感器在体积分数为80×10–6的甲醇浓度下进行多次测试灵敏度均保持在0.25左右，且在15天内均维持在较高水平。同时，在高湿度、无光照等恶劣条件下依然对甲醇有较好的响应。考虑到金属卤化钙钛矿结构可以很容易通过改变元素来调节性质，该研究方法和实验过程可应用到对其他气体的检测。Abstract: Methanol gas is toxic gas that can harm the human nerve system and blood circulation system. Developing devices capable of detecting methanol gas is of great significance. The use of sensors to detect methanol gas has the advantages of low cost, high sensitivity, and real-time monitoring. However, the mainstream methanol gas sensors mainly rely on metal oxides, which have the drawback of high operating temperatures. Therefore, we synthesized perovskite quantum dots CsPbBr3 through a simple solution synthesis method, and passivated their surface defects using an acetylacetone indium ligand (In(Acac)3), obtaining a material with good gas sensitivity to methanol gas at room temperature. The sensitivity to a volume fraction of 80×10–6 methanol gas at room temperature is 0.25, and the response/recovery time is 11.0 s/17.0 s, gas sensitivity is further improved under ultraviolet light irradiation. It also has good reproducibility and stability, the sensitivity of the sensor has been maintained at around 0.25 after multiple tests at a volume fraction of 80×10–6 methanol gas, and the sensor sensitivity has remained at a high level for 15 days. At the same time, it still has a good response to methanol gas under harsh conditions such as high humidity and no light. Considering that the structure of metal halide perovskite can easily adjust its properties by changing elements, this research method and experimental process can be applied to the detection of other gases.
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Key words:
- perovskite /
- gas sensor /
- methanol /
- metal organic compounds /
- coordination modification
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图 1 CsPbBr3-In薄膜制备以及气体传感器制备流程
Figure 1. CsPbBr3-In thin film preparation and gas sensor preparation process
FTO—F doped SnO2 conductive glass
图 2 (a) CsPbBr3-In晶体结构和传感器组成图；(b) CsPbBr3-In量子点、CsPbBr3量子点和标准CsPbBr3卡片XRD图谱；((c), (d)) CsPbBr3-In薄膜的SEM、EDS图像；((e), (f)) CsPbBr3-In量子点的TEM、HRTEM图像
Figure 2. (a) CsPbBr3-In crystal structure and sensor composition diagram; (b) CsPbBr3-In quantum dots, CsPbBr3 quantum dots, and standard CsPbBr3 card XRD patterns; ((c), (d)) SEM and EDS images of CsPbBr3-In thin films; ((e), (f)) TEM and HRTEM images of CsPbBr3-In quantum dots
图 3 CsPbBr3和CsPbBr3-In薄膜的XPS图谱：(a) Cs3d；(b) Pb4f；(c) Br3d；(d) In3d；(e) O1s； (f) 全谱
Figure 3. XPS spectra of CsPbBr3 and CsPbBr3-In film: (a) Cs3d; (b) Pb4f; (c) Br3d; (d) In3d; (e) O1s; (f) Full spectra
图 4 CsPbBr3-In和CsPbBr3薄膜的光学表征：(a) 荧光光谱(PL)；(b) 时间分辨荧光光谱(TRPL)；(c) 紫外可见吸收光谱(UV-vis)
Figure 4. Optical characterization of CsPbBr3-In and CsPbBr3 film:(a) Photoluminescence (PL) spectra; (b) Time-resolution photoluminescence (TRPL) spectra; (c) UV-vis spectra
图 5 CsPbBr3-In在室温下的传感性能：(a) 甲醇体积分数为80×10–6下传感器多次响应曲线；(b) 甲醇体积分数为80×10–6下甲醇的响应恢复时间；(c) CsPbBr3-In传感器对不同浓度甲醇的灵敏度；(d) CsPbBr3传感器对不同浓度甲醇的灵敏度；(e) CsPbBr3-In、CsPbBr3传感器对低浓度甲醇气体的响应曲线；(f) CsPbBr3-In传感器在空气中的稳定性
Figure 5. Sensing performance of CsPbBr3-In at room temperature: (a) Multiple response curve of the sensor at a volume fraction of 80×10–6 methanol gas; (b) Response recovery time of methanol at a volume fraction of 80×10–6; (c) Sensitivity of CsPbBr3-In sensor to different concentrations of methanol; (d) Sensitivity of CsPbBr3 sensor to different concentrations of methanol; (e) Response curve of CsPbBr3-In, CsPbBr3 sensor to low concentrations of methanol gas; (f) Stability of CsPbBr3-In sensor in air
tres—Response time; trec—Recovery time; R0—Starting resistance; R—Real time resistance
图 6 CsPbBr3-In传感器在不同光照条件下的响应(气体浓度：体积分数80×10–6)：(a) 传感器在黑暗条件下对甲醇气体的响应；(b) 传感器在自然光照射下对甲醇气体的响应；(c) 传感器在紫外光照射下对甲醇气体的响应；(d) 传感器在自然光+紫外灯对甲醇气体的响应
Figure 6. Response of CsPbBr3-In sensor under different light conditions (Gas concentration: 80×10–6): (a) Response of sensor to methanol gas under dark conditions; (b) Response of sensor to methanol gas under natural light irradiation; (c) Response of sensor to methanol gas under ultraviolet light irradiation; (d) Response of sensor under natural light+ultraviolet lamp
图 7 传感器对对不同气体和不同湿度环境下的响应情况：((a), (b)) 传感器对体积分数为80×10–6不同气体的灵敏度、响应恢复时间测试；((c), (d)) 传感器在不同湿度条件下对体积分数为80×10–6甲醇气体的响应
Figure 7. Sensor response to different gases and humidity environments: ((a), (b)) Sensor sensitivity and response/recovery time test for different gases with a volume fraction of 80×10–6; ((c), (d)) Response of the sensor to a volume fraction of 80×10–6 methanol gas under different humidity conditions
表 1 用于甲醇检测的各种纳米结构金属氧化物的比较
Table 1. Comparison of various nanostructured metal oxides for methanol detection
Material Temperature/℃ Concentration Sensitivity (R0/R) tres/trec/s Ref. CsPbBr3-In RT 80×10–6 1.33 11/17 This work SnO2 200 100×10–6 58 4/8 [33] CoFe2O4 90 100×10–6 1.42 430/252 [34] Zn2SnO4 450 50×10–6 2.25 39/138 [35] MoS2/TiO2 240 200×10–6 1.8 80/100 [36] In/NiO 300 200×10–6 10.9 273/26 [37] Note: RT—Room temperature. 
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