半導體接面的種類很多，像是同質異型接面或是異質異型接面，這些都是由少數載子的擴散主導電流的流動，免不了會有少數載子與多數載子複合現象的發生，而異質同型接面又因兩側為不同材料，而在接面處會有缺陷或是晶格不匹配發生，若能製作出接面兩側為同種材料，並由多數載子來主導電流流動的接面，便能有效降低少數載子與多數載子複合現象的發生，因此有了同質同型接面(isotype homojunction)概念的產生，而實踐的方法是利用摻雜方法去調整半導體費米能階的位置，在接面處因為兩側費米能階的差，仍會使能帶有些微的彎曲(bending)。
在評估許多摻雜的方法像是熱擴散法、離子佈植、電漿摻雜法之後，我們決定利用原子層沉積臨場摻雜(in-situ Atomic Layer Deposition)技術去作摻雜，因為原子層沉積不僅能利用自我侷限效應精準地控制薄膜厚度，還能成長出許多種高品質且薄的透明導電薄膜像是氧化鋅(ZnO)、摻鋁氧化鋅(AZO)、摻鎵氧化鋅(GZO)、氧化鋁(Al2O3)等等。
因此本篇論文以原子層沉積臨場摻雜的方法，去調控不同濃度的摻鎵氧化鋅，驗證此方式能夠控制半導體的費米能階，進而成長氧化鋅與不同濃度的摻鎵氧化鋅接面，並將其應用在電晶體的製作上。實驗結果顯示在特定偏壓下，共射極電流增益(common emitter current gain)最大可逼近49480，在同樣偏壓下量測到的共基極電流增益(common-base current gain)幾乎等於1。而透過元件實際的電流圖，推導出的基極區傳輸因數(base transport factor)也穩定座落於0.98以上。另一方面我們也探討此電晶體作為光感測用途時的表現，在鹵素燈照光功率為100μW的情況下，本論文電晶體的電壓響應度最高可以達到10475V/W、電流響應度最高可以達到308mA/W。

There are two kinds of anisotype semiconductor junctions, namely anisotype homojunction and anisotype heterojunction. The current in these junctions are all dominated by the diffusion of minority carriers, and the recombination of minority carriers with majority carriers cannot be avoided. So, the relative long time constants related to diffusion and recombination usually limit the operation speed of devices. On the other hand, an isotype heterojunction is consisted of different materials and there are defects and lattice mismatches at the junction. If a junction is consisted of same material and the current of the junction is dominated by the majority carriers only, carrier recombination diffusion can be greatly reduced. This is the concept of isotype homojunction. To form proper energy band bending in an isotype homojunction, we adjusted the Fermi levels of the materials at the junction by doping engineering.semiconductor.
After comparing many doping methods, such as thermal diffusion, ion implantation, and plasma doping, we decided to use in-situ Atomic Layer Deposition (ALD) technique for material growth and doping. Atomic layer deposition can not only use the self-limiting effect to control the film thickness precisely, but also grow high-quality and thin transparent conductive films, such as zinc oxide (ZnO), aluminum-doped zinc oxide (AZO), gallium-doped zinc oxide (GZO), aluminum oxide (Al2O3) and so on.
Therefore, this study used in-situ atomic layer deposition method to adjust the concentrations of gallium-doped zinc oxide, verified that this method can control the Fermi level of the zinc oxide, and then grew the junction of zinc oxide and gallium-doped zinc oxide. Samples of of isotype homojunction have been realized,
and applied to the fabrication of transistors. Experimental results show that the common emitter current gain of the transistor can approximate to 49480 under a certain bias voltage. The common base current gain measured under the same bias voltage is also extremely close to 1. The base transport factor derived from the actual current pattern of the device is also stable above 0.98. In the meantime, we also studied the performance of transistors as a photo sensor. Under the exposure of halogen lamp (Power=100μW), the maximum voltage responsivity of this device can achieve 10475V/W, and the current responsivity can reach 308mA/W.

摘要 I
Abstract II
致謝 IV
目錄 VI
圖目錄 IX
表目錄 XII
第一章 緒論 1
1.1 前言 1
1.2 研究動機 3
1.3 文章節架構 4
第二章 半導體基本性質 5
2.1 半導體能帶性質 5
2.1.1 能帶理論 5
2.1.2 費米能階 6
2.2 半導體接面 9
2.2.1 蕭特基接觸(Schottky)與歐姆(Ohmic)接觸 9
2.2.2 同質異型接面 13
2.2.3 異質異型接面 14
2.2.4 異質同型接面 15
2.2.5 同質同型接面 16
2.3 半導體摻雜方法 16
2.3.1 半導體的摻雜 16
2.3.2 熱擴散法 17
2.3.3 離子佈植 17
2.3.4 電漿摻雜 18
第三章 原子層沉積及氧化鋅介紹 19
3.1 原子層沉積 19
3.1.1 原子層沉積介紹 19
3.1.2 原子層沉積製程 20
3.2 氧化鋅的成長與基礎特性 22
3.2.1 常見的氧化鋅成長方式 22
3.2.2 氧化鋅基本性質 22
3.2.3 氧化鋅結構 23
3.3 摻鎵氧化鋅的成長 24
3.3.1 摻鎵氧化鋅 24
3.3.2 摻鎵氧化鋅製程 25
3.3.3 摻雜製程比較 26
3.4 常見的氧化鋅檢測分析 27
3.4.1 氧化鋅薄膜檢測 27
3.4.2 X光繞射儀(X-ray Diffraction, XRD) 27
3.4.3 X光反射儀(X-ray Reflectivity, XRR) 28
第四章 光感測器介紹 30
4.1 光感測器基本介紹 30
4.2 光二極體原理 30
4.3 光電晶體原理 31
4.4 光感測器特性 35
4.4.1 量子效率(Quantum efficiency) 35
4.4.2 響應度(Responsivity) 36
4.4.3 暗電流與雜訊 (Dark current & Noise) 37
第五章 元件設計與製作 39
5.1兩端元件—P+矽基板/氧化鋅 與 P+矽基板/摻鎵氧化鋅 39
5.1.1 元件設計與架構 39
5.1.2 元件製程 40
5.2兩端元件—氧化鋅/摻鎵氧化鋅同質同型接面 42
5.2.1 元件設計與架構 42
5.2.2 元件製程 43
5.3 三端元件—n型矽/氧化鋅/摻鎵氧化鋅 44
5.3.1 元件設計與架構 44
5.3.2 元件製程 45
第六章 量測結果與討論 47
6.1 量測儀器簡介 47
6.2 量測結果與討論 48
6.2.1 兩端元件—P+矽基板/氧化鋅 與 P+矽基板/摻鎵氧化鋅 48
6.2.2 兩端元件—氧化鋅/摻鎵氧化鋅同質同型接面 53
6.2.3 三端元件—n型矽/氧化鋅/摻鎵氧化鋅 57
第七章 結論 76
7.1結論 76
參考文獻 78

[1] K. Shiraishi, Y. Aizawa, and S. Kawakami, "Beam expanding fiber using thermal diffusion of the dopant," Journal of Lightwave Technology, vol. 8, no. 8, pp. 1151-1161, 1990, doi: 10.1109/50.57835.
[2] L. N. Large and R. W. Bicknell, "Ion-implantation doping of semiconductors," Journal of Materials Science, vol. 2, no. 6, pp. 589-609, 1967/11/01 1967, doi: 10.1007/BF00752224.
[3] B. Mizuno, I. Nakayama, M. Takase, H. Nakaoka, and M. Kubota, "Plasma doping for silicon," Surface and Coatings Technology, vol. 85, no. 1, pp. 51-55, 1996/11/01/ 1996, doi: 10.1016/0257-8972(96)02881-2.
[4] 黃政銘, 原子層沉積技術臨場摻鋁氧化鋅薄膜之製備與應用研究. 國立交通大學, 2016.
[5] A. Yamada, B. Sang, and M. Konagai, "Atomic layer deposition of ZnO transparent conducting oxides," Applied Surface Science, vol. 112, pp. 216-222, 1997/03/01/ 1997, doi: 10.1016/S0169-4332(96)01022-7.
[6] S. Sinha and S. K. Sarkar, "ZnO as transparent conducting oxide by Atomic Layer Deposition," in 2013 IEEE 39th Photovoltaic Specialists Conference (PVSC), 16-21 June 2013 2013, pp. 1183-1186, doi: 10.1109/PVSC.2013.6744351.
[7] P. R. Chalker et al., "Atomic layer deposition of Ga-doped ZnO transparent conducting oxide substrates for CdTe-based photovoltaics," Journal of Vacuum Science & Technology A, vol. 31, no. 1, p. 01A120, 2013/01/01 2012, doi: 10.1116/1.4765642.
[8] D.-J. Lee, H.-M. Kim, J.-Y. Kwon, H. Choi, S.-H. Kim, and K.-B. Kim, "Structural and Electrical Properties of Atomic Layer Deposited Al-Doped ZnO Films," Advanced Functional Materials, vol. 21, no. 3, pp. 448-455, 2011/02/08 2011, doi: 10.1002/adfm.201001342.
[9] N. P. Dasgupta, S. Neubert, W. Lee, O. Trejo, J.-R. Lee, and F. B. Prinz, "Atomic Layer Deposition of Al-doped ZnO Films: Effect of Grain Orientation on Conductivity," Chemistry of Materials, vol. 22, no. 16, pp. 4769-4775, 2010/08/24 2010, doi: 10.1021/cm101227h.
[10] S. Jakschik, U. Schroeder, T. Hecht, M. Gutsche, H. Seidl, and J. W. Bartha, "Crystallization behavior of thin ALD-Al2O3 films," Thin Solid Films, vol. 425, no. 1, pp. 216-220, 2003/02/03/ 2003, doi: 10.1016/S0040-6090(02)01262-2.
[11] M. B. Hall, "Valence shell electron pair repulsions and the Pauli exclusion principle," Journal of the American Chemical Society, vol. 100, no. 20, pp. 6333-6338, 1978/09/01 1978, doi: 10.1021/ja00488a007.
[12] "Wikipedia - Electronic band structure," Link:https://en.wikipedia.org/wiki/Electronic_band_structure.
[13] J. A. T. Suntola, "T. Suntola, J. Antson, U. S. Patent No. 4058430, DOI (1977)."
[14] 曾柏憲, 利用原子層沉積法成長出高品質摻鋁氧化鋅薄膜於矽光學元件之應用. 國立新竹教育大學, 2016.
[15] J. G. Lu, T. Kawaharamura, H. Nishinaka, Y. Kamada, T. Ohshima, and S. Fujita, "Zno-based thin films synthesized by atmospheric pressure mist chemical vapor deposition," Journal of Crystal Growth, vol. 299, no. 1, pp. 1-10, 2007/02/01/ 2007, doi: 10.1016/j.jcrysgro.2006.10.251.
[16] M. Rusu et al., "High-Efficient ZnO/PVD-CdS/Cu(In,Ga)Se2 Thin Film Solar Cells: Formation of the Buffer-Absorber Interface and Transport Properties," MRS Proceedings, vol. 865, p. F14.25, 2005, Art no. F14.25, doi: 10.1557/PROC-865-F14.25.
[17] K. Komatsu, Y. Seno, T. Komiyama, Y. Chonan, H. Yamaguchi, and T. Aoyama, "Characteristics of ZnO/CuO heterojunctions formed by direct bonding and PLD with bias voltage application," physica status solidi c, vol. 10, no. 10, pp. 1280-1283, 2013/10/01 2013, doi: 10.1002/pssc.201200963.
[18] D. Hu, Y. J. Liu, H. S. Li, X. Y. Cai, X. L. Yan, and Y. D. Wang, "Effect of nickel doping on structural, morphological and optical properties of sol–gel spin coated ZnO films," Materials Technology, vol. 27, no. 3, pp. 243-250, 2012/07/01 2012, doi: 10.1179/1753555712Y.0000000006.
[19] D. C. Look, "Progress in ZnO materials and devices," Journal of Electronic Materials, vol. 35, no. 6, pp. 1299-1305, 2006/06/01 2006, doi: 10.1007/s11664-006-0258-y.
[20] S. J. Pearton, D. P. Norton, K. Ip, Y. W. Heo, and T. Steiner, "Recent progress in processing and properties of ZnO," Superlattices and Microstructures, vol. 34, no. 1, pp. 3-32, 2003/07/01/ 2003, doi: 10.1016/S0749-6036(03)00093-4.
[21] H. T. Quang et al., "In Situ Observations of Free-Standing Graphene-like Mono- and Bilayer ZnO Membranes," ACS Nano, vol. 9, no. 11, pp. 11408-11413, 2015/11/24 2015, doi: 10.1021/acsnano.5b05481.
[22] T. H. Kim, Y.-G. Ju, L. S. Park, S. H. Lee, J. H. Baek, and Y. M. Yu, "Enhanced Optical Output Power of Tunnel Junction GaN-Based Light Emitting Diodes with Transparent Conducting Al and Ga-Codoped ZnO Thin Films," Japanese Journal of Applied Physics, vol. 49, no. 9, p. 091002, 2010/09/21 2010, doi: 10.1143/jjap.49.091002.
[23] S. D. Ponja, S. Sathasivam, I. P. Parkin, and C. J. Carmalt, "Highly conductive and transparent gallium doped zinc oxide thin films via chemical vapor deposition," Scientific Reports, vol. 10, no. 1, p. 638, 2020/01/20 2020, doi: 10.1038/s41598-020-57532-7.
[24] U. Schulz, A. Nowotnik, S. Kunkel, and G. Reiter, "Effect of processing and interface on the durability of single and bilayer 7YSZ / gadolinium zirconate EB-PVD thermal barrier coatings," Surface and Coatings Technology, vol. 381, p. 125107, 2020/01/15/ 2020, doi: 10.1016/j.surfcoat.2019.125107.
[25] X. Li et al., "Effect of oxygen pressure on GZO film as active layer of the TFT fabricated at room temperature," Superlattices and Microstructures, vol. 137, p. 106317, 2020/01/01/ 2020, doi: 10.1016/j.spmi.2019.106317.
[26] J.-H. Seo et al., "Thermal diffusion boron doping of single-crystal natural diamond," Journal of Applied Physics, vol. 119, no. 20, p. 205703, 2016/05/28 2016, doi: 10.1063/1.4949327.
[27] R. B. Fair, J. J. Wortman, and J. Liu, "Modeling Rapid Thermal Diffusion of Arsenic and Boron in Silicon," Journal of The Electrochemical Society, vol. 131, no. 10, pp. 2387-2394, 1984/10/01 1984, doi: 10.1149/1.2115263.
[28] O. W. Holland, B. R. Appleton, and J. Narayan, "Ion implantation damage and annealing in germanium," Journal of Applied Physics, vol. 54, no. 5, pp. 2295-2301, 1983/05/01 1983, doi: 10.1063/1.332385.
[29] T. Narita, T. Kachi, K. Kataoka, and T. Uesugi, "P-type doping of GaN (000bar{1}) by magnesium ion implantation," Applied Physics Express, vol. 10, no. 1, p. 016501, 2016/12/01 2016, doi: 10.7567/apex.10.016501.
[30] B. H. Kang, W.-G. Kim, J. Chung, J. H. Lee, and H. J. Kim, "Simple Hydrogen Plasma Doping Process of Amorphous Indium Gallium Zinc Oxide-Based Phototransistors for Visible Light Detection," ACS Applied Materials & Interfaces, vol. 10, no. 8, pp. 7223-7230, 2018/02/28 2018, doi: 10.1021/acsami.7b17897.
[31] T. Izumida et al., "Advantage of Plasma Doping for Source/Drain Extension in Bulk Fin Field Effect Transistor," Japanese Journal of Applied Physics, vol. 50, no. 4, p. 04DC15, 2011/04/20 2011, doi: 10.1143/jjap.50.04dc15.
[32] 蔡尚祐, 利用原子層沉積法臨場摻雜鋁氧化鋅薄膜披覆于氧化鋅奈米線之結構與光電特性研究. 國立交通大學, 2015.
[33] 余樹楨, 晶體之結構與性質. 渤海堂文化, 2009.
[34] C. Y. Chen, B. L. Kasper, and H. M. Cox, "High‐sensitivity Ga0.47In0.53As photoconductive detectors prepared by vapor phase epitaxy," Applied Physics Letters, vol. 44, no. 12, pp. 1142-1144, 1984/06/15 1984, doi: 10.1063/1.94670.
[35] M. Tyagi, M. Tomar, and V. Gupta, "P-N Junction of NiO Thin Film for Photonic Devices," IEEE Electron Device Letters, vol. 34, no. 1, pp. 81-83, 2013, doi: 10.1109/LED.2012.2223653.
[36] H. Liu and R. Huang, "All-Transparent Zinc Oxide-Based Phototransistor by Mist Atmospheric Pressure Chemical Vapor Deposition," IEEE Electron Device Letters, vol. 40, no. 2, pp. 243-246, 2019, doi: 10.1109/LED.2018.2889057.
[37] Z. Pei, H. Lai, J. Wang, W. Chiang, and C. Chen, "High-Responsivity and High-Sensitivity Graphene Dots/a-IGZO Thin-Film Phototransistor," IEEE Electron Device Letters, vol. 36, no. 1, pp. 44-46, 2015, doi: 10.1109/LED.2014.2368773.
[38] H. Zan, S. Kao, and S. Ouyang, "Pentacene-Based Organic Phototransistor With High Sensitivity to Weak Light and Wide Dynamic Range," IEEE Electron Device Letters, vol. 31, no. 2, pp. 135-137, 2010, doi: 10.1109/LED.2009.2037591.
[39] A. Khosropour and A. Sazonov, "Hydrogenated Nanocrystalline Silicon Near Infrared Photodiode Detector," IEEE Electron Device Letters, vol. 35, no. 11, pp. 1106-1108, 2014, doi: 10.1109/LED.2014.2358559.
[40] C. S. Yin, "The p-i-n junction-surface depletion-layer photodiode," IEEE Electron Device Letters, vol. 12, no. 8, pp. 442-443, 1991, doi: 10.1109/55.119159.
[41] M.-K. L. Simon M. Sze, Semiconductor Devices: Physics and Technology. John Wiley & Sons, 2008.
[42] D. F. Swinehart, "The Beer-Lambert Law," Journal of Chemical Education, vol. 39, no. 7, p. 333, 1962/07/01 1962, doi: 10.1021/ed039p333.
[43] 孫晨維, 矽/石墨烯/氧化鋅異質接面電晶體之研究. 國立清華大學, 2018.
[44] 吳承平, 新穎矽/石墨烯/單層氧化鋅異質接面電晶體之製作與特性研究. 國立清華大學, 2019.
[45] C. M. Torres et al., "High-Current Gain Two-Dimensional MoS2-Base Hot-Electron Transistors," Nano Letters, vol. 15, no. 12, pp. 7905-7912, 2015/12/09 2015, doi: 10.1021/acs.nanolett.5b03768.