溶液製程聚苯胺摻雜銅離子之硫化氫感測器

硫化氫為腐蝕性、酸性、急性劇毒氣體，高濃度暴露下短時間內能使人致命，低濃度暴露也將對眼睛、呼吸道系統及中樞神經系統造成影響，近年來開始流行以導電高分子來製作氣體感測器，本論文使用半導體製程，搭配導電高分子溶液製程有機電子元件，採用聚苯胺為感測基底，並摻雜硝酸銅作為感測材料，形成一電阻式氣體感測器，複合材料滴鑄沉積於金電極間通道，達到低成本、快速製程，相較於其他導電高分子所摻雜鹽類劇毒且對人體有害，硝酸銅更佳環境友善！透過摻雜硝酸銅離子，暴露完硫化氫後導電度顯著上升。感測濃度鎖定即將對人體產生危害之區間3~15 ppm，5 ppm 於五分鐘內反應量高達20 %之高靈敏度，元件在一般室溫環境下操作，並可於各溼度區間偵測硫化氫之存在。感測器之選擇性測試中，硫化氫反應量遠大於氣體如二氧化碳、一氧化碳和乙烯，二氧化氮可觀察到電阻反向地上升趨勢。此外，感測器如遇溼度單獨參予亦被討論，可藉由另一溼度感測器之加入，溼度之辨別將更為準確，此方式可解決有機高分子選擇性受水分子影響之問題。最後利用拉曼光譜儀、可見光紫外光光譜儀、偏光顯微鏡和X 光繞射光譜儀來驗證感測機制。

關鍵字

有機電子元件；電阻式硫化氫感測器；導電高分子；聚苯胺/硝酸銅複合材料；溶液製成；滴鑄沉積

並列摘要

In this thesis, an organic electronic element is fabricated by semiconductor manufacturing process combining with solution process of conducting polymer.Polyaniline (Emeraldine Salt) was chosen for polymer matrix, then doping with copper nitrate as sensing material formed a chemiresisive gas sensor. Drop casting the composite between the gold electrodes achieves fast fabrication, low cost, and nontoxicity which is either safe for human or environmental friendly comparing to other doping salts of polyaniline. With copper ions can improve sensitivity significantly. The detection range targets at above 3 ppm H2S which can do damage to human body. On exposure to 5 ppm H2S, the decrease of resistance is up to 20 % in 5 minutes. The sensing element can be operated at room temperature with the linear response from 3 to 15 ppm range and suitable for discriminating concentration in different relative humidity. Sensors selectivity is higher than carbon monoxide, carbon dioxide, and ethylene. A decrease of conductivity was observed when injecting nitrogen dioxide. In addition, in the condition which the humidity individually exists and participates in the response of the sensor was discussed. By means of adding additional humidity sensor which can more accurately determinate H2S and solve the disadvantage of conducting polymer which is often sensitive to humidity. In the final section, the sensing mechanism was verified by material analysis including Raman spectroscopy, UV-VIS, polarizing microscopy and XRD.

並列關鍵字

Organic electronic devices ； chemiresistive hydrogen sulfide sensors ； conducting polymer ； polyaniline emeraldine salt/copper nitrate composite ； solution process ； drop casting

參考文獻

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[6] C. D. Pearson and W. J. Hines, "Determination of Hydrogen-Sulfide, Carbonyl Sulfide, Carbon-Disulfide, and Sulfur-Dioxide in Gases and Hydrocarbon Streams by Gas Chromatography Flame Photometric Detection," Analytical Chemistry, vol. 49, pp. 123-126, 1977.

[7] L. M. Webber, K. H. Karmarkar, and G. G. Guilbault, "Coated Piezoelectric Crystal Detector for Selective Detection and Determination of Hydrogen-Sulfide in Atmosphere," Analytica Chimica Acta, vol. 97, pp. 29-35, 1978.

[8] J. F. Vetelino, R. K. Lade, and R. S. Falconer, "Hydrogen-Sulfide Surface Acoustic-Wave Gas Detector," Ieee Transactions on Ultrasonics Ferroelectrics and Frequency Control, vol. 34, pp. 156-161, Mar 1987.

[10] G. Neri, "First Fifty Years of Chemoresistive Gas Sensors," Chemosensors, vol. 3, pp. 1-20, Mar 2015.

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溶液製程聚苯胺摻雜銅離子之硫化氫感測器

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