以E-gun蒸鍍系統鍍製Sn、Zn、Cu前驅層，分子束蒸鍍系統鍍製Se前驅層，再以RTP(rapid thermal process)快速硒化製程反應成CZTSe。調變前驅物設定之組成比，能成功得到接近單一相之CZTSe。單一相範圍為Zn/Sn=1.0，0.5≦Cu/(Zn+Sn)≦0.75，Se/(Zn+Sn+Cu)=1.2。
相同製程下，以濺鍍系統鍍製Sn、Zn、Cu前驅層，製作之CZTSe。無論調整設定之Zn/Sn比，或Cu/(Zn+Sn)比。皆無法再現實驗室接近單一相CZTSe。推測組成已嚴重偏移。
藉由改變Cu/(Zn+Sn)比，能調整CZTSe之電阻率。Cu/(Zn+Sn)比愈高，電阻率愈低。設定Cu/(Zn+Sn)比範圍為0.75≧Cu/(Zn+Sn)≧0.50，可得到電阻率範圍為0.03 Ω-cm ~2400 Ω-cm。成功得到高電阻與低電阻之CZTSe。

The single-phase CZTSe films can be synthesized with the preset composition of Zn/Sn=1.0, 0.5≦Cu/(Zn+Sn)≦0.75, Se/(Cu+Zn+Sn)=1.2. The Sn, Zn and Cu precursors were deposited with the E-gun evaporator system, and the Se precursor was deposited with the Molecular Beam evaporator system. Using a rapid thermal process, the precursors reacted to form single phase CZTSe films.
Previous results indicated that using the sputter system, it was possible to successfully synthesize CZTSe single phase films. More recent attempts to synthesize single phase CZTSe films with the sputter system to deposit Cu, Zn, and Sn failed.
Increasing the Cu/(Zn+Sn) ratio reduced the resistivity of CZTSe. Resistivities between 0.03 Ω-cm ~2400 Ω-cm were achieved with compositions of 0.75≧Cu/(Zn+Sn)≧0.50.

論文審定書 i
誌謝 ii
中文摘要 iii
英文摘要 iv
第一章 簡介 1
1.1 前言 1
1.2太陽電池原理 2
1.3 研究動機與目的 6
第二章 文獻回顧 7
2.1 Cu2ZnSnSe4的晶體結構 7
2.2 Cu2ZnSnSe4之點缺陷 9
2.3 Cu2ZnSnSe4的薄膜電阻率 13
2.4金屬前驅層疊層順序 16
2.5 Cu2ZnSnSe4硒化反應機制 18
2.6 Cu2ZnSnSe4二次相判定 19
第三章 實驗流程與儀器介紹 22
3.1 CZTSe薄膜製備 22
3.2 CZTSe元件製作 25
3.3實驗儀器與分析儀器介紹 26
第四章 實驗結果與討論 36
4.1三吋濺鍍系統鍍製CZTSe 37
4.1.1觀察前驅層 38
4.1.2組成調變 40
4.1.3後續檢討 44
4.2 E-gun蒸鍍系統鍍製CZTSe 46
4.2.1前驅層準備 46
4.2.2組成調變 54
4.2.3雙層CZTSe 61
第五章 結論 64
第六章 參考文獻 66

[1] 宋慶軍、熊卓， 太陽能電池串聯和並聯電阻問題的探討。
[2] A. Walsh, S. Chen, S.H. Wei , and X.G. Gong, Kesterite Thin-Film Solar Cells:
Advances in Materials Modelling of Cu2ZnSnS4, Advanced Energy Material 2; 400-
409(2012)
[3] A. Khare, B. Himmetoglu, M. Johnson, D. J. Norris, M. Cococcioni, Calculation of the lattice dynamics and Raman spectra of copper zinc tin chalcogenides and comparison to experiments, Journal of Applied Physics 111,083707(2012)
[4] S. Nakamura, T. Maeda, and T. Wada, Phase Stability and Electronic Structure of In-Free Photovoltaic Materials Cu2IISnSe4 (II: Zn, Cd, Hg), Japanese Journal of Applied Physics 50,05FF01 (2011)
[5] T. Maeda, S. Nakamura, and T. Wada, “Phase Stability and Electronic Structure of In-Free Photovoltaic Semicondoctors, Cu2ZnSnSe4 and Cu2ZnSnS4 by first-pinciples calcuiation, MRS Proceedings Volume 1165 (2009)
[6] G. Zoppi, I. Forbes, R.W. Miles, P.J. Dale, J.J. Scragg, L.M. Peter, Progress in Photovoltaics: Research and Applications 17, 315 (2009)
[7]T. Maeda, S. Nakamura, T. Wada, First-principles calculations of vacancy formation in In-free photovoltaic semiconductor Cu2ZnSnSe4, Thin Solid Films5197513-7516(2011)
[8] S. Chen, A. Walsh X. G. Gong, and S. H. Wei, Classification of Lattice Defects in the Kesterite Cu2ZnSnS4 and Cu2ZnSnSe4 Earth-Abundant Solar Cell Absorbers, Material Research Society 25,1522 (2011)
[9] S. Chen, X. G. Gong, A. Walsh and S. H. Wei, Structural, Electronic and Defect Properties of Cu2ZnSn(S, Se)4 Alloys, Material Research Society(2011)
[10] S. Ahn, S. Jung, J. Gwak, A. Cho, K. Shin, K. Yoon, D. Park, H. Cheong, and J. H. Yun, Determination of band gap energy (Eg) of Cu2ZnSnSe4 thin films: On the discrepancies of reported band gap values, Appl. Phys 97, 021905 (2010).
[11] S.M. Lee, Y.S. Cho, “Characteristics of Cu2ZnSnSe4 and Cu2ZnSn(Se,S)4 absorber thin films prepared by post selenization and sequential sulfurization
of co-evaporated Cu–Zn–Sn precursors”, Journal of Alloys and Compounds 579 (2013) 279–283.
[12] G.S. Babu, Y.B.K. Kumar, P.U. Bhaskar and V.S. Raja,“Effect of post-deposition annealing on the growth of Cu2ZnSnSe4 thin films for a solar cell absorber layer”, Semicond. Sci. Technol. 23 (2008) 085023 (12pp).
[13] S.Chen, X. G. Gong, A. Walsh and S. H. Wei, “Crystal and electronic band structure of Cu2ZnSnX4 (X=S and Se) photovoltaic absorbers: First-principles insights”, Applied Physics Letters 94, 041903 (2009).
[14] T. Tanaka, T. Sueishi, K. Saito, Q. Guo, M. Nishio, K. M. Yu, and W.Walukiewicz，Existence and removal of Cu2Se second phase in coevaporated Cu2ZnSnSe4 thin films，Journal of Applied Physics 111, 053522 (2012)
[15] K. Tanaka, Y. Fukui, N. Moritake, H. Uchiki, Chemical composition dependence of morphological and optical properties of Cu2ZnSnS4 thin films deposited by sol–gel sulfurization and Cu2ZnSnS4 thin film solar cell efficiency, Solar Energy Materials & Solar Cells 95 (2011) 838–842
[16] C. Platzer-Bj orkman , J.Scragg,H.Flammersberger,T.Kubart,M.Edoff, Influence of precursor sulfur content on film formation and compositional changes in Cu2ZnSnS4 films and solar cells, Solar Energy Materials & Solar Cells 98 (2012) 110–117
[17] S. Chen, X. G. Gong, A. Walsh, and S.-H. Wei, Defect physics of the kesterite thin-film solar cell absorber Cu2ZnSnS4, APPLIED PHYSICS LETTERS 96, 021902 _2010_
[18] I. Repins , C. Beall , N. Vora , C. D .Hart , D. Kuciauskas , P. Dippo , B. To , J. Mann , W. C. Hsu , A. Goodrich , R. Noufi, Co-evaporatedCu2ZnSnSe4 films anddevices, Solar Energy Materials & Solar Cells 101 (2012) 154–159
[19] T. Tanaka, T. Sueishi, K. Saito, Q. Guo, M. Nishio, K. M. Yu, and W.Walukiewicz，Existence and removal of Cu2Se second phase in coevaporated Cu2ZnSnSe4 thin films，Journal of Applied Physics 111, 053522 (2012)
[20] P A Fernandes, P M P Salomé and A F da Cunha, Precursors' order effect on the properties of sulfurized Cu2ZnSnS4thin films, Semicond. Sci. Technol. 24 105013 (7pp) (2009).
[21] Andrew Fairbrother , Lionel Fourdrinier , Xavier Fontané , Victor Izquierdo-Roca , Mirjana Dimitrievska , Alejandro Pérez-Rodríguez , and Edgardo Saucedo , Precursor Stack Ordering Effects in Cu2ZnSnSe4 Thin Films Prepared by Rapid Thermal Processing, J. Phys. Chem. C, 2014, 118 (31), pp 17291–17298
[22] 葉智為，以快速硒化法製備Cu2ZnSnSe4薄膜並用於太陽電池之製作，國立中山大學材料科學研究所碩士論文(2014)
[23] 高千惠，Cu2ZnSnSe4薄膜之快速硒化製程研究，國立中山大學材料科學研究所碩士論文(2012)
[24] S. Chen, L. Wang, A. Walsh,G. Gong and S. H. Wei, Abundance of CuZn+SnZn and 2CuZn+SnZn defect clusters in kesterite solar cells, Applied Physics Letters,101(22),223901(2012)
[25] A. Nagaoka,K. Yoshino, H. Taniguchi,T. Taniyama, H. Miyake, Growth of Cu2ZnSnSe4 single crystals from Sn solutions, Journal of Crystal Growth 354(1):147–151(2012).
[26] N. B. Mortazavi Amiri, A. V. Postnikov, Secondary phase Cu2SnSe3 vs. kesterite Cu2ZnSnSe4: similarities and differences in lattice vibration modes. J. Appl. Phys. 112, 033719 (2012)
[27] K. Muska, M. Kauk, M. Grossberg, M. Altosaar, J. Raudoja, O. Volobujeva, Influence of compositional deviations on the properties of Cu2ZnSnSe4 monograin powders, Energy Procedia10, 323-327 (2011).
[28] G. M. Ilari , C. M. Fella, C. Ziegler, A. R. Uhl, Y. E. Romanyukn , A. N. Tiwari, Cu2ZnSnSe4 solar cell absorbers spin-coated fromamine-containing ether solutions, Solar Energy Materials and Solar Cells 104, 125-130 (2012).
[29] A. Redinger, K. Hönes, X. Fontané, V. I. Roca, E. Saucedo, Detection of a ZnSe secondary phase in coevaporated Cu2ZnSnSe4 thin Films, Applied Physics Letters 98, 101907 (2011).
[30] Nirav Vora, Jeffrey Blackburn, Ingrid Repins, Carolyn Beall, Bobby To, Joel Pankow, Glenn Teeter, Matthew Young, and Rommel Noufi,“Phase identification and control of thin films deposited by co-evaporation of elemental Cu, Zn, Sn, and Se”, Journal of Vacuum Science & Technology A 30, 051201 (2012); doi: 10.1116/1.4732529
[31] 羅聖全，研發奈米科技的基本工具之一 電子顯微鏡介紹-SEM