一般熱蒸鍍法係使用熱擴散方式將銅薄膜擴散進入硫化鎘層，但此方法尚有濃度梯度分布均勻等問題。本論文針對熱蒸鍍法所造成之濃度梯度問題改以共蒸鍍法製備硫化鎘發光二極體，目的是希望藉共蒸鍍法讓p-type摻銅硫化鎘薄膜內的銅濃度均勻一致。調控不同硫化鎘蒸鍍速率條件與銅粒進行共蒸鍍，藉此改變p-type摻銅硫化鎘薄膜內之銅濃度，並探討鍍膜速率對薄膜堆積情形，表面型態、晶粒大小、光學特性之影響。以低鍍率蒸鍍硫化鎘薄膜可以得到表面平整的薄膜，顆粒堆積大小均勻，且其PL放光強度也佳。以RTA在100 ℃下熱處理摻銅硫化鎘薄膜內之銅原子使銅更均勻分布，同時激發銅原子之活性。共蒸鍍法製備之硫化鎘發光二極體元件，在適當RTA熱處理溫度與時間下，可以降低漏電流；RTA熱處理也可降低元件之串聯電阻。從實驗結果顯示硫化鎘最佳鍍膜速率為4 Å/s，同時進行後續元件之製備並量測其發光及二極體特性。但可能元件中存有過多非輻射複合中心，造成非輻射複合機率增加導致元件無法通電發光。

Thermal evaporation method was employed to prepare CdS(Cu)/CdS films via a layer by layer deposition of CdS and Cu, following with thermal annealing to prompt the diffusion of Cu into CdS layer, thus reducing the influence of concentration gradient of Cu in p-type CdS(Cu) layer. The study is aimed at manufacturing CdS(Cu)/CdS light-emitting diode device by co-evaporation method. Co-evaporation method is used to fabricate the device with various ratios of Cd to Cu, so as to control the concerntration of Cu in p-type CdS(Cu) thin film. The UV-vis analysis shows that the absorption wavelength is at about 510 ~ 530 nm. The PL intensity decreases as the ratio of CdS to Cu increases. And the SEM images show that the surface morphology is much more uniform than that fabricated by thermal evaporation method, this may lead to a better junction of p-type CdS(Cu) and n-type CdS layers. Rapid Thermal Annealing (RTA) is used to activate Cu atom in p-type thin film during the fabricating process by heating the film at 100 ℃ for 5 minutes. Based on the results of surface morphology, XRD analysis, photoluminescence and UV absorption, 4 Å/s is chosen to be the best condition. The characteristic of diode can be observed in CdS(Cu)/CdS diodes prepared by co-evaporation method. Proper RTA can reduce the leakage current between p-n junction, however, there detects no light emitting form the device. It might be due to the present of too many non-radiation recombination centers in the films so as to decrease the radiation probability, then leading to no light emitting.

[1]孫培真、黃建晃，生活科技教育月刊 ”新世代節能環保照明－白光LED”，高雄師範大學，台灣，p.104 2005。
[2] M. G. Craford, “Visible Light-Emitting Diodes: Past, Present, and Very Bright Future” MRS bull. Vol.25 (10) p.27 2000
[3] N. Holonyak Jr. and S. F. Bevaqua, “Coherent (Visible) Light Emission From Ga(As1−xPx) Junctions” Appl. Phys. Lett., Vol.1 (4) p.82 1962
[4] M. G. Craford, “LED Challenge th Incandescents” IEEE Circuits Devices Mag. Vol.8 (5) p.24 1992
[5] N. Savage, “LED Light the Future” Technology Review Vol.103 (5) p.38 2000
[6]陳澤澎，工業材料 “發光二極體的發展及¬¬¬¬¬¬新應用”，工業技術研究院，台灣，p.74 1997
[7] N. Holonyak, Jr., S. F. Bevacque, C. V. Bielan, and S. J. Lubowski, “The ‘Direct-Indirect’ Transition in Ga(As1-xPx) p-n junctions” Appl. Phys. Lett. Vol.3 (3) p.1 1963
[8] D. G. Thomas, J. J. Hopfield, and C. J. Frosch, “Isoelectronic Traps Due to Nitrogen in Gallium Phosphide” Phys. Rev. Lett. Vol.15 (22) p.857 1965
[9] M. J. Chou, D. C. Tsui, and G. Weimann, “Negative Photoconductivity of Two-dimensional Holes in GaAs/AlGaAs Heterojuncions” Appl. Phys. Lett. Vol.47 (6) p.609 1985
[10] M. A. Hasse, J. Qiu, J. M. Depuyde, and H. Cheng, “Blue-green Laser Diodes” Appl. Phys. Lett. Vol.59 (11) p.1272 1991
[11] S. Nakamura, K. Kitamura, H. Umeya, A. Jia, M. Kobayashi, A. Yoshikawa, M. Shimotomai, Y. Kato, and K. Takahashi, “Bright Electroluminescence from CdS Quantum Dot LED Structure” Electron. Lett. Vol.34 (25) p.2435 1998¬
[12] A. Ishibashi, “II-VI Blue-green Light Emitters” J. Cryst. Growth Vol.159 p.555 1996
[13] S. M. Sze., ”Physics of Semiconductor Devices” Wiley Interscience Publication, New York, 1981
[14] U. V. Desnica, “Doping Limits in II-VI Compounds - Challenges, Problems and Solutions” Prog. Cryst. Growth Charact. Mater. Vol.36 (4) p.291 1998
[15] Landholt-Boernstein 1982
[16] W. W. Anderson and J. T. Mitchell, “Phosphorous-Ion-Implanted CdS” J. Appl. Phys. Vol.12 (10) p.334 1968
[17] P. J. Sebastian, “P‐type CdS Thin Films Formed by In Situ Cu Doping in the Chemical Bath” J. Appl. Phys. Vol.62 (23) p.2956 1995
[18] S. Spiering, L. Bürkert, D. Hariskos, M. Powalla, B. Dimmler, C. Giesen, M. Heuken and M. Heuken, “MOCVD Indium Sulphide for Application as a Buffer Layer in CIGS Solar Cells” Thin Solid Films Vol.517 (7) p.2328 2009
[19] H. Murai, T. Abe, J. Matsuda , H. Sato, S. Chiba, Y. Kashiwaba, “Improvement in the light emission characteristics of CdS:Cu/CdS diodes” Appl. Surf. Sci. Vol.244 p.351 2005
[20] T. Abe, J. Sato, S. Ohashi, M. Watanabe and Y. Kashiwaba, “Light Emission of a CdS(Cu)/CdS Thin Film Diode” Phys. Status Solidi B Vol.229 (2) p.1015 2002
[21] Y. Kashiwaba, J. Sato and T. Abe, “Emission of lights of various colors from p-CdS : Cu/n-CdS thin-film diodes” Appl. Surf. Sci. Vol.212 p.162 2003
[22] Kashiwaba Y., Isojima K., Ohta K., “Improvement in the Efficiency of Cu-doped CdS/non-doped CdS Photovoltaic Cells Fabricated by an All-vacuum Process” Sol. Energy Mater. Sol. Cells Vol.75 p. 219 2003
[23] P. K. Ghosh, U. N. Maiti, Sk. F. Ahmed, K. K. Chattopadhyay, “Highly Conducting Transparent Nanocrystalline Cd1-xSnxS Thin Film Synthesized by RF Magnetron Sputtering and Studies on Its Optical, Electrical and Field Emission Properties” Sol. Energy Mater. Sol. Cells Vol.90 (16) p.2616 2006
[24] N. de la Rosa-Fox, R. Erce-Montilla, M. Pinero and L. Esquivias, “Controlled size of PbS nanocrystals doped ORMOSIL” Opt. Mater. Vol.22 (1) p.1 2003
[25] S. M. Song and S. Y. Choi, “Spin-coated Ge-Se-Te Si3N4-CdS chalconitride Thin Film” J. Non-Cryst. Vol.291 p.50 2001
[26] S. Coe, W. K. Woo, M. Bawend, and V. Bulovic, “Electroluminescence from Single Monolayers of Nanocrystals in Molecular Organic Devices” Nature Vol.420 6917 p.800 2002
[27] D. B. Mitzi, L. L. Kosbar, C. E. Murray, M. Copel, and A. Afzali, “High-mobility Ultrathin Semiconducting Films Prepared by Spin Coating“ Nature Vol.428 6980 p.299 2004
[28] Z. Y. Pan, X. G. Peng, T. J. Li and J. Z. Liu, “Controlled Growth of the Size-quantized CdS at The Interface of the Stearic Acid Langmuir-Blodgett Films” Appl. Surf. Sci. Vol.108 (4) p.439 1997
[29] P. Facci, V. Erokhin, A. Tronin, and C. Nicolini, “Formation of Ultrathin Semiconductor Films by CdS Nanostructure Aggregation” J. Phys. Chem. Vol.98 (50) p.13323 1994
[30] M. M. Islam, S. Ishizuka, A. Yamada, K. Sakurai, S. Niki, T. Sakurai, and K. Akimoto, “CIGS Solar Cell with MBE-grown ZnS Buffer Layer” Sol. Energy Mater. Sol. Cells Vol.93 p.970 2009
[31] A. R. Long and A. M. MacLeod, “Co-evaporation Control System for Two-component Alloys” J. Phys.E: Sci. Instrum. Vol.12 (3) p.205 1979
[32] K. H.Kim, K. H. Yoon, J. H. Yun, and B. T. Ahn, “Effect of Se Flux on the Microstructure of Cu(In, Ga)Se2 Thin Film Deposited by a Three-Stage Co-evaporation Process” Electrochem. Solid-State Lett. Vol.9 (3B) p.A382 2006
[33] 吳旭晟，利用旋轉塗佈法及熱蒸鍍法製備硫化鎘及摻銅硫化鎘半導體薄膜，國立成功大學碩士論文，台灣，2008
[34] 陳璟文，以熱蒸鍍法製備摻銅硫化鎘/硫化鎘發光二極體元件暨微波加熱製備碲化鎘量子點之研究，國立成功大學碩士論文，台灣，2009
[35] R. A. Pearman，陳世昌 譯，固態工業電子學，東華書局，1986
[36] B. G. Streetman and S. Banerjee, Solid state electronic devices, N.J. :Prentice Hall, Upper Saddle River, 2000
[37] M. V. Artemyev, S. V. Gaponenko, I. N. Germanenko, and A. M. Kapitonov, “Irreversible Photochemical Spectral Hole-burning in Quantum-sized CdS Nanocrystals Embedded in a Polymeric Film“ Chem. Phys. Lett. Vol.243 p.450 1995
[38] A. P. Alivisatos, “Semiconductor Clusters, Nanocrystals, and Quantum Dots” Science Vol.271 (5251) p. 933 1996
[39] N. M. Park, T. S. Kim, and S. J. Park, “Band Gap Engineering of Amorphous Silicon Quantum Dots for Light-emitting Diodes” Appl. Phys. Lett. Vol.78 (17) p.23 2001
[40] L. E. Brus, “A Simple Model for the Ionization Potential, Electron Affinity, and Aqueous Redox Potentials of Small Semiconductor Crystallites” J. Chem. Phys. Vol.79 (11) p.5566 1983
[41] John H. Davies, The physics of low-dimensional semiconductors, Cambridge University Press, Cambridge, p.1-3, 13, 46, 107 1998
[42] L. E. Brus, “Electron-electron and Electron-hole Interactions in Small Semiconductor Crystallites: The Size Dependence of the Lowest Excited Electronic States” J. Chem. Phys. Vol.80 (9) p.4403 1984
[43] L. Brus, “Zero-dimensional Excition in Semiconductor Clusters” IEEE J. Quantum Electron. Vol.22 (9) p.1909 1986
[44]伍秀菁、汪若文、林美吟 編，真空技術與應用，國家科學研究院儀器科學研究中心，台灣，2001
[45]陳寶清，表面工業雜誌 “真空表面處理工學”，表面工業，台灣，1992
[46]賴耿陽，真空蒸鍍應用技術，復漢出版社，台灣，1991
[47] J. A. Venables and G. L. Price, ed. J. W. Matthews, Nucleation of thin films in Epitaxial Growth, New York, Academic Press, p381 1975
[48] V. E. Bauer, Phanomenologische theorie der kristallabscheidung an oberflachen I, Zeitschrift fur Kristallographie, Bd. 110, p.372 1958
[49] J. A. Venables, G. D. T. Spiller and M. Hanbucken, “Nucleation and Growth of Thin Film” Rep. Prog. Phys. Vol.47 (4) p.399 1984
[50] 林鴻明、曾世杰，奈米半導體材料之特殊氣體感測性質，工業材料，台灣，p.163 2000
[51] A. Schmidt, M. L. Anderson, and N. R. Armstrong, “Electronic Stages of Vapor Deposited Electron and Hole Transport Agents and Luminescent Materials for Light Emitting Diodes” J. Appl. Phys. Vol.78 (9) p.5619 1995
[52] Donald A. Neamen, Semiconductor physics and Devices: Basic Principles, McGraw-Hill, New York, 2003
[53] B. D. Cullity, “Elements of X-ray Diffraction” NJ :Prentice Hall, Upper Saddle River, p.102 2001
[54] J. D. Finegan and R. W. Hoffman, “Stress Anisotropy in Evaporated Iron Films” J. Appl. Phys. Vol.30 (4) p.597 1959
[55] R. W. Hoffman, in physical of nonmetallic Thin films, edited by C.H.S. Dupuy and A. Cachard, Plenum Press: New York,pp.273 (1969).
[56] R. W. Hoffman, F. J. Anders and E. C. Crittenden, “Evidence for Collapse of Lattice Vacancy Aggregates to Form Dislocation Rings” J. Appl. Phys. Vol.24 (2) p.231 1953
[57] R. W. Hoffman and H. S. Story, “Stress Annealing in Copper Films” J. Appl. Phys. Vol.27 (2) p.193 1956
[58] E. Fred Schubert, “Light-Emitting Diode” Cambridge University Press, New York, 2003
[59] C. X. Wang, G. W. Yang, H. W. Liu, Y. H. Han, J. F. Luo, C. X. Gao and G. T. Zou, “Experimental Analysis and Theoretical Model for Anomalously High Ideality Factors in ZnO/diamond p-n Junction Diode” Appl. Phys. Lett. Vol.84 (13) p.2427 2004
[60] 黃肇瑞、郭建麟、王瑞琪、劉全璞，p-n型氧化亞銅/氧化鋅異質接面奈米線陣列的合成與性質分析，成大研發快訊，第14卷，第6期，2010