原子層沉積技術係利用化學前驅物與樣品表面之化學吸附現象和前驅物本身自我限制之特色，使透過原子層沉積技術所沉積之薄膜有著高覆蓋性、高薄膜品質之優點，由於半導體元件大小、線寬等不斷微縮、構造趨於複雜，使得化學氣項沉積技術已不符合現在製程之要求，原子層沉積技術之優勢將更顯著，對於未來半導體製程之品質將有著顯著之提升。
本研究以合作廠商 馗鼎奈米科技進行系統設計開發並由學生進行系統規格評估與製程驗證之產學合作方式進行，以氧化鋁作為目標之規格膜層，進行原子層沉積系統之製程驗證，於第一部分探討氧化鋁薄膜沉積之製程參數，發現TMA與H2O於脈衝量為15 mTorr、沖洗時間分別為60 s及90 s、輸送溫度105 ˚C、製程溫度200 ~ 300 ˚C時，薄膜沉積速率符合原子層沉積模式達1.42 Å/cycle、不均勻性達1.6 %、薄膜折射率達1.6、薄膜粗糙度達0.6 nm之高品質鍍膜。第二部分為探討以原子層沉積技術沉積氧化鋁薄膜是否能達原子層磊晶，但研究發現製程溫度提高至系統之最高溫度500 ˚C，所得之氧化鋁薄膜於XRD分析結果未能為有氧化鋁之訊號，因此推斷為非晶薄膜，不屬於原子層磊晶。

The continuous downscaling of complementary metal oxide semiconductor devices has required the atomic layer deposition (ALD). This study was carried out in the form of industry-academia cooperation to develop an ALD system. Al2O3 was selected as the targeted film. In the first part, the process parameters of Al2O3 deposition were discussed. It was found that the GPC would reach 1.42 Å/cycle, the non-uniformity was 1.6 %, the n value was 1.6, the roughness was 0.6 nm, and the ALD window was between 200 ˚C and 300 ˚C with TMA and H2O pulse volume of 15 mTorr, the purge length of 60 s and 90 s, the delivery temperature of 105 ˚C. In the second part, I explored whether Al2O3 deposited by ALD could achieve atomic layer epitaxy (ALE). However, the Al2O3 was still amorphous by the XRD analysis when process temperature was increased to the maximum temperature of 500 ˚C. Although the Al2O3 of ALD was not the ALE, this study had already developed an ALD system successfully with good Al2O3 quality by industry-academia cooperation.

[1] K. Natori, "Ballistic metal‐oxide‐semiconductor field effect transistor," Journal of Applied Physics, vol. 76, no. 8, pp. 4879-4890, 1994.
[2] J. Robertson, "Band offsets of wide-band-gap oxides and implications for future electronic devices," Journal of Vacuum Science & Technology B: Microelectronics and Nanometer Structures Processing, Measurement, and Phenomena, vol. 18, no. 3, pp. 1785-1791, 2000.
[3] J. Robertson, "High dielectric constant gate oxides for metal oxide Si transistors," Reports on progress in Physics, vol. 69, no. 2, p. 327, 2005.
[4] J. Robertson and R. M. Wallace, "High-K materials and metal gates for CMOS applications," Materials Science and Engineering: R: Reports, vol. 88, pp. 1-41, 2015.
[5] K. J. Yang and C. Hu, "MOS capacitance measurements for high-leakage thin dielectrics," IEEE Transactions on Electron Devices, vol. 46, no. 7, pp. 1500-1501, 1999.
[6] J. Caruge, J. E. Halpert, V. Wood, V. Bulović, and M. Bawendi, "Colloidal quantum-dot light-emitting diodes with metal-oxide charge transport layers," Nature photonics, vol. 2, no. 4, pp. 247-250, 2008.
[7] J.-M. Caruge, J. E. Halpert, V. Bulović, and M. G. Bawendi, "NiO as an inorganic hole-transporting layer in quantum-dot light-emitting devices," Nano letters, vol. 6, no. 12, pp. 2991-2994, 2006.
[8] W. Ji, S. Liu, H. Zhang, R. Wang, W. Xie, and H. Zhang, "Ultrasonic spray processed, highly efficient all-inorganic quantum-dot light-emitting diodes," ACS Photonics, vol. 4, no. 5, pp. 1271-1278, 2017.
[9] X. Dai et al., "Solution-processed, high-performance light-emitting diodes based on quantum dots," Nature, vol. 515, no. 7525, pp. 96-99, 2014.
[10] W. Ji et al., "Efficient quantum dot light-emitting diodes by controlling the carrier accumulation and exciton formation," ACS applied materials & interfaces, vol. 6, no. 16, pp. 14001-14007, 2014.
[11] W. Ji, H. Shen, H. Zhang, Z. Kang, and H. Zhang, "Over 800% efficiency enhancement of all-inorganic quantum-dot light emitting diodes with an ultrathin alumina passivating layer," Nanoscale, vol. 10, no. 23, pp. 11103-11109, 2018.
[12] R. Bosco, J. Van Den Beucken, S. Leeuwenburgh, and J. Jansen, "Surface engineering for bone implants: a trend from passive to active surfaces," Coatings, vol. 2, no. 3, pp. 95-119, 2012.
[13] R. NEWBERY, "Ion Plating Technology–Developments and Applications," ed: Taylor & Francis, 1988.
[14] J. Melskens, "Optimisation of a protocrystalline hydrogenated amorphous silicon top solar cell for highest stabilised efficiency," 2007.
[15] 薄膜科学与技术手册. 机械工业出版社, 1991.
[16] J. Antson and T. Suntola, "Method for producing compound thin films," US Patent, vol. 4, no. 058,430, 1977.
[17] 章詠湟, 陳智, and 彭智龍, "原子層沉積系統原理及其應用," (in 繁體中文), 科儀新知, no. 159, pp. 33-43, 2007.
[18] M. R. Saleem, R. Ali, M. B. Khan, S. Honkanen, and J. Turunen, "Impact of atomic layer deposition to nanophotonic structures and devices," Frontiers in Materials, vol. 1, p. 18, 2014.
[19] Y. Lu, C. Hsieh, and G. Su, "The Role of ALD-ZnO Seed Layers in the Growth of ZnO Nanorods for Hydrogen Sensing," Micromachines, vol. 10, no. 7, p. 491, 2019.
[20] M. Ritala, "Advanced ALE processes of amorphous and polycrystalline films," Applied surface science, vol. 112, pp. 223-230, 1997.
[21] L. Niinistö, M. Nieminen, J. Päiväsaari, J. Niinistö, M. Putkonen, and M. Nieminen, "Advanced electronic and optoelectronic materials by Atomic Layer Deposition: An overview with special emphasis on recent progress in processing of high‐k dielectrics and other oxide materials," physica status solidi (a), vol. 201, no. 7, pp. 1443-1452, 2004.
[22] T. S. Suntola, A. J. Pakkala, and S. G. Lindfors, "Apparatus for performing growth of compound thin films," ed: Google Patents, 1983.
[23] W. He, "ALD: Atomic Layer Deposition Precise and Conformal Coating for Better Performance," Handbook of Manufacturing Engineering and Technology; Springer-Verlag, London, vol. 5, pp. 2964-2966, 2015.
[24] L. Nyns, A. Delabie, J. Swerts, S. Van Elshocht, and S. De Gendt, "ALD and parasitic growth characteristics of the tetrakisethylmethylamino hafnium (TEMAH)/H2O process," Journal of The Electrochemical Society, vol. 157, no. 11, pp. G225-G229, 2010.
[25] M. Leskelä and M. Ritala, "Atomic layer deposition (ALD): from precursors to thin film structures," Thin solid films, vol. 409, no. 1, pp. 138-146, 2002.
[26] S. M. George, B. Yoon, and A. A. Dameron, "Surface Chemistry for Molecular Layer Deposition of Organic and Hybrid Organic− Inorganic Polymers," Accounts of chemical research, vol. 42, no. 4, pp. 498-508, 2009.
[27] S. M. George, "Atomic layer deposition: an overview," Chemical reviews, vol. 110, no. 1, pp. 111-131, 2010.
[28] A. Foroughi-Abari and K. C. Cadien, "In situ spectroscopic ellipsometry study of plasma-enhanced ALD of Al2O3 on chromium substrates," Journal of The Electrochemical Society, vol. 159, no. 2, p. D59, 2011.
[29] E. Guziewicz et al., "ALD grown zinc oxide with controllable electrical properties," Semiconductor Science and Technology, vol. 27, no. 7, p. 074011, 2012.
[30] M. Gebhard et al., "PEALD of SiO2 and Al2O3 thin films on polypropylene: Investigations of the film growth at the interface, stress, and gas barrier properties of dyads," ACS applied materials & interfaces, vol. 10, no. 8, pp. 7422-7434, 2018.
[31] J. Zhang, H. Yang, Q.-l. Zhang, S. Dong, and J. Luo, "Structural, optical, electrical and resistive switching properties of ZnO thin films deposited by thermal and plasma-enhanced atomic layer deposition," Applied surface science, vol. 282, pp. 390-395, 2013.
[32] 電漿工學的基礎. 復文, 1986.
[33] C. San Wong and R. Mongkolnavin, Elements of plasma technology. Springer, 2016.
[34] 黃世明 and S.-M. Huang, "以熱燈絲化學氣相沉積法成長鑽石及奈米鑽石薄膜."
[35] B. Chapman, "Glow Discharge Processes, John Wiley & Sons," New York, 1980.
[36] A. Fridman and L. A. Kennedy, Plasma physics and engineering. CRC press, 2004.
[37] K. Nojiri, Dry etching technology for semiconductors. Springer, 2015.
[38] J. Roth, "Industrial Plasma Engineering Volume 1 Principles. Bristol and Philadelphia," Institute of Physics publishing, 1995.
[39] T. Suntola and J. Antson, "US Patent 4058430, 1977," There is no corresponding record for this reference.[Google Scholar], 1996.
[40] P. Poodt et al., "Spatial atomic layer deposition: A route towards further industrialization of atomic layer deposition," Journal of Vacuum Science & Technology A: Vacuum, Surfaces, and Films, vol. 30, no. 1, p. 010802, 2012.
[41] E. Dickey and W. Barrow, "52nd Annual Technical Conference Proceedings of the Society of Vacuum Coaters," Santa Clara, CA,(Society of Vacuum Coaters, Albuquerque, NM, 2009), pp. 720-726, 2009.
[42] P. Maydannik, T. Kääriäinen, and D. Cameron, "An atomic layer deposition process for moving flexible substrates," Chemical Engineering Journal, vol. 171, no. 1, pp. 345-349, 2011.
[43] D. H. Levy, S. F. Nelson, and D. Freeman, "Oxide electronics by spatial atomic layer deposition," Journal of Display Technology, vol. 5, no. 12, pp. 484-494, 2009.
[44] D. H. Levy, D. Freeman, S. F. Nelson, P. J. Cowdery-Corvan, and L. M. Irving, "Stable ZnO thin film transistors by fast open air atomic layer deposition," Applied Physics Letters, vol. 92, no. 19, p. 192101, 2008.
[45] A. Vermeer, F. Roozeboom, P. Poodt, and R. Gortzen, "High throughput, low cost deposition of alumina passivation layers by spatial atomic layer deposition," MRS Online Proceedings Library Archive, vol. 1323, 2011.
[46] P. Poodt, A. Lankhorst, F. Roozeboom, K. Spee, D. Maas, and A. Vermeer, "High‐speed spatial atomic‐layer deposition of aluminum oxide layers for solar cell passivation," Advanced materials, vol. 22, no. 32, pp. 3564-3567, 2010.
[47] A. Illiberi, R. Scherpenborg, Y. Wu, F. Roozeboom, and P. Poodt, "Spatial Atmospheric Atomic Layer Deposition of Al x Zn1–x O," ACS applied materials & interfaces, vol. 5, no. 24, pp. 13124-13128, 2013.
[48] A. Illiberi, F. Roozeboom, and P. Poodt, "Spatial atomic layer deposition of zinc oxide thin films," ACS applied materials & interfaces, vol. 4, no. 1, pp. 268-272, 2012.
[49] H.-J. Kim and S.-M. Nam, "High loading of nanostructured ceramics in polymer composite thick films by aerosol deposition," Nanoscale research letters, vol. 7, no. 1, pp. 1-6, 2012.