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研究生:賴奎璋
研究生(外文):Kuei-Chang Lai
論文名稱:矽烷化合物的改質於無電鍍鎳(磷)沉積之單晶矽研究
論文名稱(外文):Study of electroless nickel(phosphorus) deposited on a silane-compound modified silicon wafer
指導教授:陳志銘陳志銘引用關係
指導教授(外文):Chih-Ming Chen
口試委員:馮憲平衛子健
口試委員(外文):Hsien-Ping FengTzu-Chien Wei
口試日期:2015-07-14
學位類別:碩士
校院名稱:國立中興大學
系所名稱:化學工程學系所
學門:工程學門
學類:化學工程學類
論文種類:學術論文
論文出版年:2015
畢業學年度:103
語文別:中文
論文頁數:83
中文關鍵詞:太陽能電池正面金屬化快速退火程序鎳矽化何物
外文關鍵詞:Front Contact Metallization of Silicon Solar CellRapid Thermal AnnealingNickel Silicide
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矽晶太陽能電池發展至今已經五十餘年,在正面金屬化製程中,網印銀線製程因低電阻、低操作難度、適合大量生產等特性而被廣泛利用,然而近年來銀價持續飆漲,除了降低銀膠中銀漿的比例外,以價格較便宜的銅取代銀膠作為導線的概念逐漸受到重視。雖然銅具有低電阻、低電遷移、熱傳導性佳等特性,但銅原子的擴散係數相當大,在高溫甚至室溫環境下皆容易擴散至矽基板,進而破壞PN junction結構,造成電池效率下降,因此實務設計上勢必要在銅層與矽基板之間增加一層擴散阻障層防止銅原子擴散,此擴散阻障層需具備性質穩定、電性佳兩種特性,一般來說,可分大略為乾式製程(PVD&CVD)與濕式製程(電鍍、無電電鍍)兩種製備方式,但因商業化製程須顧及生產成本,本研究探討以濕式製程所製之無電電鍍鎳磷層做為擴散阻障層。
本研究嘗試以ETAS+PVP-nPd改質之酸性無電鍍鎳磷層作為擴散阻障層,在第一部分的討論中會探討鍍層在快速退火500~900℃後界面是否會生成較低電阻的鎳矽化合物,吾人發現退火溫度在700℃以下時,界面並沒有任何生成物生成,鍍層為Ni與Ni3P結晶,當退火溫度達800℃時界面才有NiSi與NiSi2生成,此時鍍層的晶相也因鎳原子與磷原子的組成改變而形成Ni12P5與Ni2P,在此溫度下附著力提升至10.93 MPa。另外,除了退火溫度外,浸泡ETAS溶液後的清洗程序會直接影響到退火後鎳矽化合物的生成量與覆蓋率,經由製程上的改良,吾人可將鎳矽化合物的覆蓋率從17.4%提升到69.6%。
第二部分則是為了模擬電池在實際操作條件下的耐用度所做的長效老化實驗,以高溫的環境(200℃)加速銅原子擴散,探討無電鍍鎳磷層是否能在此溫度條件下阻擋銅原子,其結果顯示無電鍍鎳磷層在此條件下處理1000小時後依然沒有銅原子擴散至矽基材中。


Silicon solar cell has now developed 50 years. Screen printing of silver paste has been widely used in front contact of Si-based solar cell. However, as the constantly increasing price of silver, copper was considered as a cheaper and practical solution of this critical issue. Although copper has low resistivity, low electric migration property, and good thermal conductivity, benefit to electron transmission, it can form copper silicide easily during annealing process, which has high resistivity and may destroy the P-N junction. It is necessary to add a diffusion barrier in order to prevent such aging reaction. There are two largely field to form a interconnect layer between copper and substrate. One is the dry process such as PVD&CVD. The other is the wet process such as electroplating and electroless deposition.
In this work, we use ETAS modified + PVP-nPd activated electroless nickel as diffusion barrier. In the first part, we discuss about the phase formation of the Ni(P)/Si system after rapid thermal annealing at 500~900℃. There are only crystal Ni and Ni3P after annealing 500 to 700℃, non of nickel silicide were formed. The nickel silicide such as NiSi&NiSi2 were observed after RTP-800℃. The electroless deposit layer become Ni12P5 and Ni2P due to composition change of the ration of nickel and phosphorus. The adhesion raise to 10.93 MPa after RTP 800℃. In addition, the cleaning process which is after the substrate immersed into ETAS solution play an important role in coverage and quality of nickel silicide. The coverage change from 17.4% to 69.6% after our process modification.
In the second part, in order to discuss about the diffusion barrier property of electroless nickel layer, we used 200℃ oven in order to simulate the aging effect when the silicon solar cell is exposed to the real operation condition. The results show that there is no copper atom diffused into the substrate after 1000 h aging test.


摘要 i
Abstract ii
致謝 iii
總目錄 iv
圖目錄 vi
表目錄 ix
第1章 緒論 1
1.1 前言 1
1.2 研究目的與動機 3
第2章 文獻回顧 4
2.1 太陽能電池介紹 4
2.1.1 太陽能電池發電原理 4
2.1.2 矽晶太陽能電池基板 6
2.1.3 表面粗糙化與抗反射層 7
2.2 矽晶太陽能電池的效率 9
2.2.1 太陽能電池測試標準 9
2.2.2 能量轉換效率 9
2.3 無電鍍鎳沉積 12
2.3.1 無電電鍍基本原理 12
2.3.2 無電鍍鎳(Electroless nickel plationg) 原理 13
2.3.3 無電鍍鎳磷層退火處理 15
2.4 鎳矽化合物的生成 16
2.4.1 鎳矽雙成分系統相與相圖 16
2.4.2 鎳矽化合物的生長(於純鎳系統) 17
2.4.3 鎳矽化合物的生長(於無電鍍鎳系統) 21
2.5 擴散阻障層 27
第3章 實驗 30
3.1 藥品清單 30
3.2 實驗架構 31
3.3 分析方法與儀器原理 33
3.3.1 高解析X光繞射儀-低略角繞射法(Grazing incident diffraction, GI-XRD) 33
3.3.2 四點探針與傳輸線模型 34
3.3.3 附著力測試 37
3.4 實驗流程 39
3.4.1 晶片前處理: 39
3.4.2 ETAS矽烷化合物表面改質 39
3.4.3 PVP-nPd奈米粒子合成 41
3.4.4 無電鍍鎳沉積 42
3.4.5 快速退火處理程序(Rapid Thermal Process) 43
3.4.6 正面金屬化與擴散阻障層測試 44
3.5 實驗步驟總整理 46
第4章 結果與討論 48
4.1 清洗程序 48
4.2 快速熱退火處理 50
4.2.1 表面型態與相生成 50
4.2.2 矽烷化合物對退火程序的影響 60
4.3 附著力測試 67
4.4 片電阻(Sheet resistance, Rs)測試 68
4.5 擴散阻障層效果測試 70
第5章 結論與未來展望 74
5.1 結論 74
5.2 未來展望 76
參考文獻 77


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