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研究生： 李英瑋
Li, Ying-Wei
論文名稱： 硫摻雜輔助P型氧化鋅薄膜與奈米結構研究
Sulfur assisted realization of p-type Zn0 thin film and nanostructure
指導教授： 吳振名
口試委員: 李奕賢
陳世偉
學位類別： 碩士
Master
系所名稱： 工學院 - 材料科學工程學系
Materials Science and Engineering
論文出版年： 2012
畢業學年度： 100
語文別： 中文
論文頁數： 154
中文關鍵詞： 氧化鋅 、硫化製程 、P型薄膜 、Sol-gel製程
相關次數： 點閱：3  下載：0 
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    • 氧化鋅(ZnO)為ⅡⅥ族半導體材料，因為其高能隙值3.37eV及高激子束縛能60meV等材料性質，有非常多的應用領域如發光二極體、光催化材料、全透明電子元件等光電元件材料。但難以製備電性良好的p-type氧化鋅侷限了氧化鋅的發展空間，目前難以製備穩定p-type氧化鋅可以歸因於，摻雜物在氧化鋅中的溶解度太低與摻雜物活化能量太高等因素，因此如何提升溶解度與降低活化能成為很重要的課題。因此Persson et al.提出藉由摻雜等價元素硫以降低活化能的方式，希望以此降低摻雜物的活化能量。
    本研究主要分三部分，第一部分是使用硫化後氧化兩階段熱處理方式將硫摻雜到以溶膠-凝膠法(Sol-gel method)製備的氧化鋅薄膜，用各種分析儀器去驗證硫的摻雜與比較摻雜前後性質差異。第二部分是以溶膠-凝膠法製備p-type氧化鋅薄膜，實驗選用了三種不同元素鋰、銅、氮做為p-type摻雜物。觀察不同退火溫度及摻雜濃度對p-type氧化鋅電性的影響，並藉由分析晶體結構、光學性質與化學鍵結的方式去探討薄膜內部缺陷的變化去解釋電性的轉變。第三部分是將成功鍍製的p-type氧化鋅薄膜進行硫化後氧化兩階段熱處理流程，觀察此一製程對p-type氧化鋅薄膜的電性與基本材料性質造成的影響。

    目錄 摘要 I 致謝 II 目錄 IV 表目錄 VIII 圖目錄 XI 第一章 緒論 1 1-1 前言 1 1-2 研究動機 2 第二章 文獻回顧 4 2-1 氧化鋅發展簡介 4 2-2 氧化鋅本質缺陷對形成p-type氧化鋅的影響 6 2-3 使用鋰為p-type摻雜物 7 2-4 使用銅為p-type摻雜物 9 2-5 使用氮為p-type摻雜物 10 2-6 硫添加的能隙工程 12 第三章 實驗方法 26 3-1 實驗大綱 26 3-2 製備硫摻雜氧化鋅薄膜及氧化鋅奈米柱 27 3-2-1 基板準備: 27 3-2-2 Sol-gel法鍍製氧化鋅薄膜 27 3-2-3 硫化製程 27 3-2-4 氧化製程 28 3-2-5 製備氧化鋅奈米柱 28 3-3 製備p-type氧化鋅薄膜 29 3-3-1 基板準備: 29 3-3-2 Sol-gel法鍍製p-type氧化鋅薄膜 29 3-4 製備硫摻雜p-type氧化鋅薄膜 30 3-5 量測儀器 30 第四章 結果與討論 35 4-1 硫摻雜氧化鋅製備及分析 35 4-1-1 前言 35 4-1-2 熱處理溫度及硫粉量對硫化和硫化再氧化之硫摻雜氧化鋅薄膜的影響 36 4-1-3 不同氧化熱處理溫度及熱處理時間對硫化再氧化之硫摻雜氧化鋅薄膜的影響 45 4-1-4 以硫化再氧化方式熱處理氧化鋅奈米柱及其性質分析 51 4-2 以摻雜製備P型氧化鋅薄膜及性質分析 56 4-2-1 鋰摻雜氧化鋅薄膜製備及性質分析 56 4-2-2 銅摻雜氧化鋅薄膜製備及性質分析 73 4-2-3 氮摻雜氧化鋅薄膜製備及性質分析 83 4-3 P-type氧化鋅薄膜硫化再氧化之兩階段熱處理及性質分析 87 4-3-1 前言 87 4-3-2 鋰摻雜氧化鋅薄膜硫化後氧化之兩階段熱處理及性質分析 87 4-3-3 銅摻雜氧化鋅薄膜硫化後氧化之兩階段熱處理及性質分析 89 4-3-4 氮摻雜氧化鋅薄膜硫化後氧化之兩階段熱處理及性質分析 90 4-3-5 結論 92 第五章 結論 146 第六章 參考文獻 149

    1. McCluskey, M. D.; Jokela, S. J., Defects in ZnO. Journal of Applied Physics 2009, 106 (7).
    2. Janotti, A.; Van de Walle, C. G., Fundamentals of zinc oxide as a semiconductor. Reports on Progress in Physics 2009, 72 (12).
    3. H. von Wenckstern, H.; Schmidt, H.; Brandt, M.; Lajn, A.; Pickenhain, R.; Lorenz, M.; Grundmann, M.; Hofmann, D. M.; Polity, A.; Meyer, B. K.; Saal, H.; Binnewies, M.; Borger, A.; Becker, K. D.; Tikhomirov, V. A.; Jug, K., Anionic and cationic substitution in ZnO. Progress in Solid State Chemistry 2009, 37 (2-3), 153-172.
    4. Ozgur, U.; Alivov, Y. I.; Liu, C.; Teke, A.; Reshchikov, M. A.; Dogan, S.; Avrutin, V.; Cho, S. J.; Morkoc, H., A comprehensive review of ZnO materials and devices. Journal of Applied Physics 2005, 98 (4).
    5. Choi, Y. S.; Kang, J. W.; Hwang, D. K.; Park, S. J., Recent Advances in ZnO-Based Light-Emitting Diodes. Ieee Transactions on Electron Devices 2010, 57 (1), 26-41.
    6. Dutta, M.; Ghosh, T.; Basak, D., N Doping and Al-N Co-doping in Sol-Gel ZnO Films: Studies of Their Structural, Electrical, Optical, and Photoconductive Properties. Journal of Electronic Materials 2009, 38 (11), 2335-2342.
    7. Klingshirn, C.; Fallert, J.; Zhou, H.; Sartor, J.; Thiele, C.; Maier-Flaig, F.; Schneider, D.; Kalt, H., 65 years of ZnO research - old and very recent results. Physica Status Solidi B-Basic Solid State Physics 2010, 247 (6), 1424-1447.
    8. Maksimov, O., RECENT ADVANCES AND NOVEL APPROACHES OF P-TYPE DOPING OF ZINC OXIDE. Reviews on Advanced Materials Science 2010, 24 (1-2), 26-34.
    9. Bahsi, Z. B.; Oral, A. Y., Effects of Mn and Cu Edoping on the microstructures and optical properties of sol-gel derived ZnO thin films. Optical Materials 2007, 29 (6), 672-678.
    10. Ghosh, T.; Basak, D., Effect of Cu-Li Co-Doping on the Structural, Optical, and Optoelectronic Properties of Sol-Gel ZnO Thin Films. Journal of the Electrochemical Society 2009, 156 (12), H916-H920.
    11. Cao, P.; Zhao, D. X.; Shen, D. Z.; Zhang, J. Y.; Zhang, Z. Z.; Bai, Y., Cu(+)-codoping inducing the room-temperature magnetism and p-type conductivity of ZnCoO diluted magnetic semiconductor. Applied Surface Science 2009, 255 (6), 3639-3641.
    12. Wu, D. P.; Jiang, Y.; Yuan, Y. F.; Wu, J. S.; Jiang, K., ZnO-ZnS heterostructures with enhanced optical and photocatalytic properties. Journal of Nanoparticle Research 2011, 13 (7), 2875-2886.
    13. Persson, C.; Platzer-Bjorkman, C.; Malmstrom, J.; Torndahl, T.; Edoff, M., Strong valence-band offset bowing of ZnO1-xSx enhances p-type nitrogen doping of ZnO-like alloys. Physical Review Letters 2006, 97 (14).
    14. Pan, H. L.; Yao, B.; Yang, T.; Xu, Y.; Zhang, B. Y.; Liu, W. W.; Shen, D. Z., Electrical properties and stability of p-type ZnO film enhanced by alloying with S and heavy doping of Cu. Applied Physics Letters 2010, 97 (14).
    15. Chen, L. L.; He, H. P.; Ye, Z. Z.; Zeng, Y. J.; Lu, J. G.; Zhao, B. H.; Zhu, L. P., Influence of post-annealing temperature on properties of ZnO : Li thin films. Chemical Physics Letters 2006, 420 (4-6), 358-361.
    16. Yang, L. L.; Ye, Z. Z.; Zhu, L. P.; Zeng, Y. J.; Lu, Y. F.; Zhao, B. H., Fabrication of p-type ZnO thin films via DC reactive magnetron sputtering by using Na as the dopant source. Journal of Electronic Materials 2007, 36 (4), 498-501.
    17. Lu, J. G.; Zhang, Y. Z.; Ye, Z. Z.; Zeng, Y. J.; He, H. P.; Zhu, L. P.; Huang, J. Y.; Wang, L.; Yuan, J.; Zhao, B. H.; Li, X. H., Control of p- and n-type conductivities in Li-doped ZnO thin films. Applied Physics Letters 2006, 89 (11).
    18. Seghier, D.; Gislason, H. P., Shallow and deep donors in n-type ZnO characterized by admittance spectroscopy. Journal of Materials Science-Materials in Electronics 2008, 19 (8-9), 687-691.
    19. Choi, Y. S.; Kang, J. W.; Hwang, D. K.; Park, S. J., Recent Advances in ZnO-Based Light-Emitting Diodes. Ieee Transactions on Electron Devices 2010, 57 (1), 26-41.
    20. Kim, K. K.; Niki, S.; Oh, J. Y.; Song, J. O.; Seong, T. Y.; Park, S. J.; Fujita, S.; Kim, S. W., High electron concentration and mobility in Al-doped n-ZnO epilayer achieved via dopant activation using rapid-thermal annealing. Journal of Applied Physics 2005, 97 (6).
    21. Oh, M. S.; Hwang, D. K.; Seong, D. J.; Hwang, H. S.; Park, S. J.; Do Kim, E., Improvement of characteristics of Ga-doped ZnO grown by pulsed laser deposition using plasma-enhanced oxygen radicals. Journal of the Electrochemical Society 2008, 155 (9), D599-D603.
    22. Ito, N.; Sato, Y.; Song, P. K.; Kaijio, A.; Inoue, K.; Shigesato, Y., Electrical and optical properties of amorphous indium zinc oxide films. Thin Solid Films 2006, 496 (1), 99-103.
    23. Gordon, R. G., Criteria for choosing transparent conductors. Mrs Bulletin 2000, 25 (8), 52-57.
    24. Chikoidze, E.; Modreanu, M.; Sallet, V.; Gorochov, O.; Galtier, P., Electrical properties of chlorine-doped ZnO thin films grown by MOCVD. Physica Status Solidi a-Applications and Materials Science 2008, 205 (7), 1575-1579.
    25. Yang, T. H.; Chiu, K. C.; Wu, J. M., Compensation of N-Related Defects in p-Type Al-N Codoped MgZnO Films. Electrochemical and Solid State Letters 2012, 15 (5), H153-H156.
    26. Vlasenflin, T .H.; Tanaka, M., p-type conduction in ZnO dual-acceptor-doped with nitrogen and phosphorus. Solid State Communications 2007, 142 (5), 292-294.
    27. Ryu, Y. R.; Zhu, S.; Look, D. C.; Wrobel, J. M.; Jeong, H. M.; White, H. W., Synthesis of p-type ZnO films. Journal of Crystal Growth 2000, 216 (1-4), 330-334.
    28. Kanai, Y., ADMITTANCE SPECTROSCOPY OF CU-DOPED ZNO CRYSTALS. Japanese Journal of Applied Physics Part 1-Regular Papers Short Notes & Review Papers 1991, 30 (4), 703-707.
    29. Du Ahn, B.; Kang, H. S.; Kim, J. H.; Kim, G. H.; Chang, H. W.; Lee, S. Y., Synthesis and analysis of Ag-doped ZnO. Journal of Applied Physics 2006, 100 (9).
    30. Janotti, A.; Van de Walle, C. G., Oxygen vacancies in ZnO. Applied Physics Letters 2005, 87 (12).
    31. Look, D. C.; Hemsky, J. W.; Sizelove, J. R., Residual native shallow donor in ZnO. Physical Review Letters 1999, 82 (12), 2552-2555.
    32. Van de Walle, C. G., Hydrogen as a cause of doping in zinc oxide. Physical Review Letters 2000, 85 (5), 1012-1015.
    33. Oh, M. S.; Hwang, D. K.; Lim, J. H.; Choi, Y. S.; Park, S. J., Current-driven hydrogen incorporation in zinc oxide. Applied Physics Letters 2007, 91 (21).
    34. Caglar, M.; Caglar, Y.; Aksoy, S.; Ilican, S., Temperature dependence of the optical band gap and electrical conductivity of sol-gel derived undoped and Li-doped ZnO films. Applied Surface Science 2010, 256 (16), 4966-4971.
    35. Tsai, S. Y.; Hon, M. H.; Lu, Y. M., Annealing effect on conductivity behavior of Li-doped ZnO thin film and its application as ZnO-based homojunction device. Journal of Crystal Growth 2011, 326 (1), 85-89.
    36. Wang, D. Y.; Zhou, J.; Liu, G. Z., Effect of Li-doped concentration on the structure, optical and electrical properties of p-type ZnO thin films prepared by sol-gel method. Journal of Alloys and Compounds 2009, 481 (1-2), 802-805.
    37. Aksoy, S.; Caglar, Y.; Ilican, S.; Caglar, M., Sol-gel derived Li-Mg co-doped ZnO films: Preparation and characterization via XRD, XPS, FESEM. Journal of Alloys and Compounds 2012, 512 (1), 171-178.
    38. Rao, T. P.; Kumar, M. C. S., Realization of stable p-type ZnO thin films using Li-N dual acceptors. Journal of Alloys and Compounds 2011, 509 (35), 8676-8682.
    39. Yang, T. H.; Wu, J. M., Thermal stability of sol-gel p-type Al-N codoped ZnO films and electric properties of nanostructured ZnO homojunctions fabricated by spin-coating them on ZnO nanorods. Acta Materialia 2012, 60 (8), 3310-3320.
    40. Yang, T. H.; Jhou, S.; Yung, T. H.; Wei, C. N.; Bor, H. Y.; Wu, J. M., Effects of MgO on N Dissolution of p-Type Al-N Codoped MgxZn1-xO Films. Journal of the Electrochemical Society 2012, 159 (2), H140-H146.
    41. Wan, Q. X.; Chen, L. L.; Liu, G. D.; Li, D. M.; Xiong, Z. H., Theory study of Ag-S codoping in ZnO. In 3rd International Photonics and Optoelectronics Meetings, Ye, C.; Wang, Z. L.; Zhou, B., Eds. 2011; Vol. 276.
    42. Sun, L. J.; Hu, J.; He, H. Y.; Wu, X. P.; Xu, X. Q.; Lin, B. X.; Fu, Z. X.; Pan, B. C., Effects of S incorporation on Ag substitutional acceptors in ZnO:(Ag, S) thin films. Solid State Communications 2009, 149 (39-40), 1663-1665.
    43. Pan, H. L.; Yang, T.; Yao, B.; Deng, R.; Sui, R. Y.; Gao, L. L.; Shen, D. Z., Characterization and properties of ZnO1-xSx alloy films fabricated by radio-frequency magnetron sputtering. Applied Surface Science 2010, 256 (14), 4621-4625.
    44. Yan, Y. F.; Al-Jassim, M. M.; Wei, S. H., Doping of ZnO by group-IB elements. Applied Physics Letters 2006, 89 (18).
    45. Lai, Y. Q.; Kuang, S. S.; Liu, F. Y.; Yuan, Z. X.; Zhang, Z. A.; Li, Y.; Liu, J.; Wang, B.; Tang, D.; Li, J.; Liu, Y. X., Effects of Cu/In ratio of electrodeposited precursor on post-sulfurization process in fabricating quaternary CuIn(S,Se)(2) thin films. Applied Surface Science 2011, 257 (20), 8360-8365.
    46. Blomqvist, A.; Arhammar, C.; Pedersen, H.; Silvearv, F.; Norgren, S.; Ahuja, R., Understanding the catalytic effects of H2S on CVD-growth of alpha-alumina: Thermodynamic gas-phase simulations and density functional theory. Surface & Coatings Technology 2011, 206 (7), 1771-1779.
    47. De Barros, M. I.; Bouchet, J.; Raoult, I.; Le Mogne, T.; Martin, J. M.; Kasrai, M.; Yamada, Y., Friction reduction by metal sulfides in boundary lubrication studied by XPS and XANES analyses. Wear 2003, 254 (9), 863-870.
    48. Liu, W. M.; Chen, S., An investigation of the tribological behaviour of surface-modified ZnS nanoparticles in liquid paraffin. Wear 2000, 238 (2), 120-124.
    49. Deroubaix, G.; Marcus, P., X-RAY PHOTOELECTRON-SPECTROSCOPY ANALYSIS OF COPPER AND ZINC-OXIDES AND SULFIDES. Surface and Interface Analysis 1992, 18 (1), 39-46.
    50. Wardle, M. G.; Goss, J. P.; Briddon, P. R., Theory of Li in ZnO: A limitation for Li-based p-type doping. Physical Review B 2005, 71 (15).
    51. Rauch, C.; Gehlhoff, W.; Wagner, M. R.; Malguth, E.; Callsen, G.; Kirste, R.; Salameh, B.; Hoffmann, A.; Polarz, S.; Aksu, Y.; Driess, M., Lithium related deep and shallow acceptors in Li-doped ZnO nanocrystals. Journal of Applied Physics 2010, 107 (2).
    52. Fujihara, S.; Ogawa, Y.; Kasai, A., Tunable visible photoluminescence from ZnO thin films through Mg-doping and annealing. Chemistry of Materials 2004, 16 (15), 2965-2968.
    53. Meyer, B. K.; Alves, H.; Hofmann, D. M.; Kriegseis, W.; Forster, D.; Bertram, F.; Christen, J.; Hoffmann, A.; Strassburg, M.; Dworzak, M.; Haboeck, U.; Rodina, A. V., Bound exciton and donor-acceptor pair recombinations in ZnO. Physica Status Solidi B-Basic Research 2004, 241 (2), 231-260.
    54. Wang, X. H.; Yao, B.; Wei, Z. P.; Sheng, D. Z.; Zhang, Z. Z.; Li, B. H.; Lu, Y. M.; Zhao, D. X.; Zhang, J. Y.; Fan, X. W.; Guan, L. X.; Cong, C. X., Acceptor formation mechanisms determination from electrical and optical properties of p-type ZnO doped with lithium and nitrogen. J. Phys. D-Appl. Phys. 2006, 39 (21), 4568-4571.
    55. Chawla, S.; Jayanthi, K.; Khan, Z. H.; Shah, J.; Kotnala, R. K., Near UV emission and p-type conductivity in Zn1-xLixO and Zn1-xNaxO nanomaterial system. Materials & Design 2010, 31 (4), 1666-1670.
    56. Xie, W. L.; Yang, Z. Q.; Chun, H., Catalytic properties of lithium-doped ZnO catalysts used for biodiesel preparations. Industrial & Engineering Chemistry Research 2007, 46 (24), 7942-7949.
    57. Aksoy, S.; Caglar, Y.; Ilican, S.; Caglar, M., Sol-gel derived Li-Mg co-doped ZnO films: Preparation and characterization via XRD, XPS, FESEM. Journal of Alloys and Compounds 2012, 512 (1), 171-178.
    58. Herng, T. S.; Lau, S. P.; Yu, S. F.; Yang, H. Y.; Teng, K. S.; Chen, J. S., Enhancement of ferromagnetism and stability in Cu-doped ZnO by N2O annealing. Journal of Physics-Condensed Matter 2007, 19 (35).
    59. Zheng, J. H.; Song, J. L.; Li, X. J.; Jiang, Q.; Lian, J. S., Experimental and first-principle investigation of Cu-doped ZnO ferromagnetic powders. Crystal Research and Technology 2011, 46 (11), 1143-1148.
    60. Kim, G. H.; Kim, D. L.; Ahn, B. D.; Lee, S. Y.; Kim, H. J., Investigation on doping behavior of copper in ZnO thin film. Microelectronics Journal 2009, 40 (2), 272-275.

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