臺灣博碩士論文加值系統

本研究開發了新穎材料的揮發性氣體微感測器，其利用了原子級的二硫化鉬當作感測層製作出電阻式的氣體感測器，並使用了二維材料的轉印技術把原子級層的二硫化鉬轉印至由微機電技術(MEMS, Microelectromechanical Systems)製作的指叉狀金電極上，藉由量測電阻訊號來當作感測器對氣體反應的指標，成功的製作出可用於一般環境下檢測揮發性氣體的氣體感測器，在化學氣相沈積法(CVD, Chemical Vapor Deposition)成長二硫化鉬的過程中，由於原料配置的比例和薄膜成長的技術或是後端的電漿處理和表面改質等等，造成材料上面會產生不同種類及數目的空缺，經由改變溫度和光照等環境因素，並從文獻推論出空缺在二硫化鉬的氣體感測機制中扮演了重要的角色，並利用光致發光光光譜儀(Photoluminescence spectrometer)和靈敏度之間的關係來加以佐證。根據文獻，氧電漿可增加二硫化鉬薄膜表面缺陷的推論，本研究利用氧電漿技術，找出了最佳處理的時間和參數，處理過後的二硫化鉬氣體感測器具有良好的感測效能，在氣體生成系統上量測的範圍較廣。傳統的以金屬氧化物為感測材料的感測器在使用上，會設計一層加熱器，藉由加熱來增加氣體感測器的靈敏度，雖然可以有效的提升揮發性有機氣體的吸附和脫附，但在製程上需要額外設計一道光罩，而且在高溫的環境上，並不利於偵測爆炸性氣體。本研究開發出的氣體感測器能夠對能依氣體的分子結構產生不同的反應，故可應用於多種揮發性有機氣體的偵測，未來有潛力應用在環境檢測上。

A novel volatile organic compound (VOC) sensor with the MoS2 atomic-layers was developed in this research. Such sensor was made by transferring the MoS2 atomic-layers grown with the chemical vapor deposition (CVD) method onto the interdigitated electrode manufactured by microelectromechanical systems for indicating the sensing ability by the impedance change. The density of defects on the MoS2 film surface was controlled by the ratio of precursors and surface treatment. The sensing mechanism related to surface defects created was illustrated using the photoluminescence spectrometer. The surface defects were found to be increased with the increasing oxygen plasma treatment (OPT) cycles due to the increase of surface defects. An optimized number of OPT cycles was found to get the excellent gas detection performance. The treated MoS2 gas sensor exhibited the good performance, sensing range, and repeatability. The chemical compounds operated at different temperatures and intensity of light power were also observed. Traditional gas sensors utilizing metal oxide as the sensing material were typically equipped with a heater. Although the gas adsorption and desorption were increased by incorporating a heater, one more photo-masking and additional processing were required to define the heater. With the high temperature heating, it’s not desirable to integrate with CMOS-based circuits and use in explosive environment. In this work, we developed a MoS2-based gas senor which can detect methanol with high sensitivity at room temperature without the extra light-activation and react with many kinds of VOCs. Based on the structure of gas, the gas sensor has the different response that shows a great potential to the environment detection.

第一章 緒論 1
1.1前言 1
1.2研究動機 1
1.3相關文獻 2
1.3.1氣體感測器介紹 3
1.3.2二硫化鉬元件相關文獻 7
第二章 基礎理論 11
2.1二維材料 11
2.1.1石墨烯 12
2.1.2二硫化鉬 14
2.2二維材料製備 16
2.2.1機械剝離法 16
2.2.2溶液剝離法 17
2.2.3化學氣相沈積法 17
2.2.4雷射脈衝鍍膜法 18
2.3電漿技術原理 20
第三章 氣體感測器製作 21
3.1元件結構 21
3.2平面指叉狀電極 21
3.2.1基板參數 22
3.2.2電子束蒸鍍 22
3.2.3 黃光微影 24
3.2.4 金屬蝕刻 25
3.2.5 晶圓切割 26
3.3原子級二硫化鉬製備 27
3.3.1化學氣相沈積法 27
3.3.2單層材料轉印 29
3.4晶片封裝 33
3.5量測平台 34
3.5.1實驗儀器 34
3.5.2揮發性有機氣體生成系統 35
第四章 氣體量測結果和討論 40
4.1氣體量測參數定義 40
4.2氣體感測 41
4.2.1待測氣體濃度調配 41
4.2.2二硫化鉬氣體感測器對甲醇之反應 42
4.2.3二硫化鉬氣體感測機制假說 45
4.3表面進行氧氣電漿處理之二硫化鉬感測器 46
4.3.1原理 46
4.3.2以氧電漿技術進行表面改質 47
4.3.3可見光激發二硫化鉬對氣體感測影響 51
4.3.4溫度對二硫化鉬氣體感測影響 55
4.3.5氧電漿處理時間和氣體反應比較 57
4.3.6光致發光光譜儀分析表面缺陷與氣體反應程度關係 59
4.3.7量測極限比較 60
4.3.8不同揮發性有機氣體反應探討 62
第五章 結論與未來展望 64
5.1結論 64
5.2未來展望 65
參考文獻 66

[1]Tian, F., Yang, S. X., & Dong, K. (2005). Circuit and noise analysis of odorant gas sensors in an E-nose. Sensors, 5(1), 85-96.
[2]Tzeng, T. H., Kuo, C. Y., Wang, S. Y., Huang, P. K., Huang, Y. M., Hsieh, W. C., Huang, Y. J., Kuo, P. H., Yu, S. A., Lee, S. C., Tseng, Y. J., Tian, W. C., Lu, S. S. (2016). A Portable Micro Gas Chromatography System for Lung Cancer Associated Volatile Organic Compound Detection. IEEE Journal of Solid-State Circuits, 51(1), 259-272.
[3]Chou, J. (1999) Catalytic Combustible Gas Sensors. Hazardous Gas Monitors: A Practical Guide to Selection, Operation, and Applications : 37-45.
[4]Liu, X., Cheng, S., Liu, H., Hu, S., Zhang, D., Ning, H. (2012) A survey on gas sensing technology. Sensors 12.7 : 9635-9665.
[5]Chou, J. (1999) Electrochemical sensors. Hazardous Gas Monitors: A Practical Guide to Selection, Operation, and Applications: 27-35.
[6]張宏維、周鈺禎、蔡顯仁、徐慧萍、施正雄。(2007) “表面聲波氣體感測器之研製與應用”。CHEMISTRY (The Chinese Chemical Society, Taipei) 65.4 : 487-498.
[7]“ACOUSTIC WAVE SENSORS.” Avaliable: http://www.sengenuity.com/tech_ref/aws_webversion.pdf
[8]“Spectroscopy overview.” Avaliable: http://commons.wikimedia.org/wiki/File:Spectroscopy_overview.svg
[9]Radisavljevic, B., Radenovic, A., Brivio, J., Giacometti, V., & Kis, A. (2011). Single-layer MoS2 transistors. Nature nanotechnology, 6(3), 147-150.
[10]Lopez-Sanchez, O., Lembke, D., Kayci, M., Radenovic, A., & Kis, A. (2013). Ultrasensitive photodetectors based on monolayer MoS2. Nature nanotechnology, 8(7), 497-501.
[11]Tsai, M. L., Su, S. H., Chang, J. K., Tsai, D. S., Chen, C. H., Wu, C. I., Li, L. J., Chen, L. J., He, J. H. (2014). Monolayer MoS2 heterojunction solar cells. ACS Nano, 8(8), 8317-8322.
[12]Geim, A. K., & Novoselov, K. S. (2007). The rise of graphene. Nature materials,6(3), 183-191.
[13]Eda, G., Yamaguchi, H., Voiry, D., Fujita, T., Chen, M., & Chhowalla, M. (2011). Photoluminescence from chemically exfoliated MoS2. Nano letters, 11(12), 5111-5116.
[14]Zheng, J., Zhang, H., Dong, S., Liu, Y., Nai, C. T., Shin, H. S., Hu, Y. J., Liu, B. Loh, K. P. (2014). High yield exfoliation of two-dimensional chalcogenides using sodium naphthalenide. Nature communications, 5.
[15]Lee, Y. H., Zhang, X. Q., Zhang, W., Chang, M. T., Lin, C. T., Chang, K. D., Yu, Y. C., Wang, T. W., Chang, C. S., Li, L. J., Lin, T. W. (2012). Synthesis of Large‐Area MoS2 Atomic Layers with Chemical Vapor Deposition. Advanced Materials, 24(17), 2320-2325.
[16]Medina, H., Huang, C. C., Lin, H. C., Huang, Y. H., Chen, Y. Z., Yen, W. C., & Chueh, Y. L. (2015). Ultrafast Graphene Growth on Insulators via Metal‐Catalyzed Crystallization by a Laser Irradiation Process: From Laser Selection, Thickness Control to Direct Patterned Graphene Utilizing Controlled Layer Segregation Process. Small, 11(25), 3017-3027.
[17]李易珊。”指叉電容式生物感測器”。電機工程學系。國立中央大學(2000)
[18]張正義。”以奈米金單層膜保護團簇塗佈於堆疊式電極結構之揮發性有機化合物氣體感測器”。 電子工程學研究所 。國立台灣大學(2013)
[19]Chen, Y. Y., Dong, M., Qin, Z., Wen, X. D., Fan, W., & Wang, J. (2011). A DFT study on the adsorption and dissociation of methanol over MoS2 surface. Journal of Molecular Catalysis A: Chemical, 338(1), 44-50.
[20]Kim, J. S., Yoo, H. W., Choi, H. O., & Jung, H. T. (2014). Tunable Volatile Organic Compounds Sensor by Using Thiolated Ligand Conjugation on MoS2.Nano letters, 14(10), 5941-5947.
[21]Cho, B., Hahm, M. G., Choi, M., Yoon, J., Kim, A. R., Lee, Y. J., Park, S. G., Kwan, J. D., Kim, C. S., Song, M., Jeong, Y., Nam, K. S., Lee, S, Yoo, T. J., Kang, C. G., Lee, B. H., Ko, H. C., Ajayan, P. M., Kim, D. H. (2015). Charge-transfer-based gas sensing using atomic-layer MoS2. Scientific reports, 5.
[22]Nan, H., Wang, Z., Wang, W., Liang, Z., Lu, Y., Chen, Q., He, D. Tan, P., Miao, F., Wang, X., Wang, J. Ni, Z. (2014). Strong photoluminescence enhancement of MoS2 through defect engineering and oxygen bonding. ACS Nano, 8(6), 5738-5745.
[23]Late, D. J., Huang, Y. K., Liu, B., Acharya, J., Shirodkar, S. N., Luo, J., Yan, A., Charles, D., Waghmare, U. V., Dravid, V. P., Rao, C. N. R. (2013). Sensing behavior of atomically thin-layered MoS2 transistors. ACS Nano, 7(6), 4879-4891.
[24]Perkins, F. K., Friedman, A. L., Cobas, E., Campbell, P. M., Jernigan, G. G., & Jonker, B. T. (2013). Chemical vapor sensing with monolayer MoS2. Nano letters, 13(2), 668-673.
[25]Cho, S. Y., Kim, S. J., Lee, Y., Kim, J. S., Jung, W. B., Yoo, H. W., Kim, J., Jung, H. T. (2015). Highly Enhanced Gas Adsorption Properties in Vertically Aligned MoS2 Layers. ACS Nano, 9(9), 9314-9321.
[26]Santosh, K. C., Longo, R. C., Wallace, R. M., & Cho, K. (2015). Surface oxidation energetics and kinetics on MoS2 monolayer. Journal of Applied Physics, 117(13), 135301.
[27]Song, S. H., Kim, B. H., Choe, D. H., Kim, J., Kim, D. C., Lee, D. J., Kim, J. M., Chang, K. J., Jeon, S. (2015). Bandgap widening of phase quilted, 2D MoS2 by oxidative intercalation. Advanced Materials, 27(20), 3152-3158.
[28]Cho, B., Kim, A. R., Park, Y., Yoon, J., Lee, Y. J., Lee, S., Yoo, T. J., Kang, C. G., Lee, B. H., Ko, H. C., Kim, D. H. Halm, M. G. (2015). Bifunctional sensing characteristics of chemical vapor deposition synthesized atomic-layered MoS2. ACS applied materials & interfaces, 7(4), 2952-2959.
[29]Dhall, R., Neupane, M. R., Wickramaratne, D., Mecklenburg, M., Li, Z., Moore, C., Lake, R. K., Cronin, S. (2015). Direct Bandgap Transition in Many‐Layer MoS2 by Plasma‐Induced Layer Decoupling. Advanced Materials, 27(9), 1573-1578.
[30]Khondaker, S. I., & Islam, M. (2016). Bandgap Engineering of MoS2 Flakes via Oxygen Plasma: a Layer Dependent Study. The Journal of Physical Chemistry C.
[31]Brown, N. M., Cui, N., & McKinley, A. (1998). An XPS study of the surface modification of natural MoS2 following treatment in an RF-oxygen plasma. Applied surface science, 134(1), 11-21.
[32]Lim, B., Bothe, K., Voronkov, V., Falster, R., & Schmidt, J. (2011). Light-Induced Degradation of the Carrier Lifetime in N-Type Czochralski-Grown Silicon Doped with Boron and Phosphorus. In Proceedings of the 26th European Photovoltaic Solar Energy Conference, Hamburg, Germany.
[33]Li, H., Huang, M., & Cao, G. (2016). Markedly different adsorption behaviors of gas molecules on defective monolayer MoS2: a first-principles study. Physical Chemistry Chemical Physics, 18(22), 15110-15117.