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研究生:張崇綸
研究生(外文):Chang, Chung-Lun
論文名稱:鍺奈米點應用於儲能電池之機制研究與製程開發
論文名稱(外文):Study on the Mechanism and Process Development of the Application of Germanium Nano-dot in Energy Storage Battery
指導教授:柳克強
指導教授(外文):Leou, Keh-Chyang
口試委員:吳永俊王敏全
口試委員(外文):Wu, Yung-ChunWang, Min-Chuan
口試日期:2017-07-31
學位類別:碩士
校院名稱:國立清華大學
系所名稱:工程與系統科學系
學門:工程學門
學類:核子工程學類
論文種類:學術論文
論文出版年:2017
畢業學年度:105
語文別:中文
論文頁數:103
中文關鍵詞:電漿輔助化學氣相沉積法光學放射光譜儀鍺奈米點儲電層儲能電池
外文關鍵詞:PECVDOESGe nano-dotCharge storage layerEnergy storage battery
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近年來,日本開發出新型全固態結構的二次電池,名叫Battenice,其輸出密度及循環壽命都優於鋰電池,本研究將改變此二次電池結構中之儲電層製備方式,期許製作出能與半導體產品結合的新型儲能電池。本實驗儲電層的製作主要分為兩個步驟,首先藉由Plasma-enhanced chemical vapor deposition (PECVD)成長SiGe薄膜,接下來經由O2熱退火處理將Si原子氧化,Ge原子重新組合成奈米晶粒並鑲嵌於SiO2當中形成儲電層,在本研究主要目地為開發SiGe薄膜沉積及O2熱退火處理之製程,並且分析儲電層之物理性質及電特性的研究。
首先,PECVD沉積SiGe薄膜時,最直接影響薄膜特性的是成長時的電漿環境,所以使用Optical Emission Spectroscopy(OES)即時量測成長薄膜時的電漿光譜,分析特徵譜線之變化和SiGe薄膜特性之關係,結果顯示OES-ratio (Ge*/Si*)與薄膜中Ge含量隨參數的變化趨勢相似,兩者隨製程功率及RGeH4(≡〖GeH〗_4/(〖GeH〗_4+〖SiH〗_4 ))增加分別呈現下降及上升的趨勢,代表OES-ratio (Ge*/Si*)及薄膜中Ge含量具有強烈關聯性。而OES-ratio(Si/SiH)和OES-ratio(Hβ/Hα)可以定性分析電漿中的電子溫度,在改變功率(50W至100W)及RGeH4(0.2至0.33)時,兩者OES-ratio變化幅度不大,最大幅度小於7 %。最後藉由H2 fulcher分析電漿中之電子密度,結果顯示H2 fulcher隨著功率及RGeH4增加而上升,表示電漿中之電子密度也隨之上升。於薄膜沉積過程,藉由電漿特徵譜線分析可以了解在不同參數下薄膜中Ge含量及電漿特性的變化。
為了讓薄膜退火後所形成之Ge奈米點能夠彼此有效隔絕,所以薄膜Ge含量選擇30-40%範圍內,於電漿參數功率為100 W及RGeH4為0.2時所沉積之SiGe薄膜之Ge含量為34.61%,其拉曼光譜顯示此薄膜有三個主要的特徵峰,分別為非晶Ge-Ge(250 cm-1)、結晶Ge-Ge(300 cm-1)及結晶Si-Ge(420 cm-1),代表薄膜由部分非晶及結晶結構組成,接下來,經熱退火條件O2/900°C /20 min處理後所形成之儲電層其拉曼光譜的非晶Ge-Ge拉曼鋒值大幅下降,薄膜結構轉而由結晶Ge-Ge及Si-Ge組成。C-V量測方面,在施加偏壓±10 V(-10 V→10 V→-10 V)時,可得記憶視窗約2.5 V,儲存電荷數量密度約為2.15×〖10〗^12 〖cm〗^(-2),於施加±20 V時,能得到更寬的記憶視窗,代表儲電量增加,遲滯曲線的方向為順時針,判斷主要電荷來源為電洞由上電極端注入,不過將此儲電層製作成新型儲能電池結構下運作時,其充放電特性則類似一個電阻元件,並沒有儲電的效果。
In recent, Japanese companies developed a new structure of secondary cell, called “Battenice”, the output density and cycle life are better than Lithium batteries. This study will use a different process to produce the charge storage layer of battery, promising to produce a new type battery which can be combined with semiconductor products. The main procedure to produce charge storage layer in this study is to deposit SiGe film by PECVD, followed by oxygen thermal annealing treatment to oxidize Si atoms into SiO2, assemble Ge atoms to form nano-crystalline grains. Then, the physical properties and electrical characteristics of the charge storage layer are discussed.
In order to investigate the effect of plasma environment on the deposition of SiGe film, the plasma spectrum was in-situ monitored using optical emission spectrum, OES. And the relationship between the specific spectrum and the characteristics of SiGe film was analyzed. The results show that the OES-ratio (Ge*/Si*) and the Ge content in the film have the same trend as the parameter change. The OES-ratio (Ge*/Si*) and the Ge content in the film show a downward and rise trend with the process power and RGeH4(≡〖GeH〗_4/(〖GeH〗_4+〖SiH〗_4 )) increasing respectively. It means OES-ratio(Ge*/Si*) exists strong correlation to the Ge content in the film. Then, OES-ratio(Si/SiH) and OES-ratio(Hβ/Hα) can be used to analyze the electron temperature in the plasma. When changing the power (50W to 100W) and RGeH4 (0.2 to 0.33), the above two OES-ratios change a little (Maximum change is less than 7%). Finally, H2 fulcher is used to analyze the electron density in the plasma. The results show that H2 fulcher increases with power and RGeH4, indicating that the electron density in the plasma also increases. So, effect of process parameters on Ge content and plasma characteristic can be understood by the OES analysis. In order to allow the Ge nano-dots formed after the film annealing to be effectively isolated from each other, the Ge content of the film is selected to be in the range of 30 to 40%, and the Ge content of the SiGe film deposited by the plasma parameter power of 100 W and RGeH4 of 0.2 is 34.61%. The Raman spectra of this film shows three specific peaks at 250 cm-1, 300 cm-1 and 420 cm-1, respectively, corresponding to the vibration modes are amorphous Ge-Ge, crystalline Ge-Ge and Si-Ge. It indicates that the film is consisting with a portion of amorphous and crystalline. Then, the Raman peak of amorphous Ge-Ge is significantly decreased after thermal annealing treatment (O2 /900 °C/20 min). This phenomenon represents the crystallization of the film. In the C-V measurement, a memory window, 2.5 V, and storage charge number density, 2.15×〖10〗^12 〖cm〗^(-2), are observed with applying 10 volt sweep range . And it is a clockwise type hysteresis, which means that carriers from the top electrode into nano-dots embedded in insulator. However, the battery which made by this charge storage layer, the charge and discharge characteristic is similar to a resistance component, and no storage effect.
摘要 I
Abstract III
目錄 V
圖目錄 VIII
表目錄 XI
第一章 緒論 1
1-1 引言 1
1-2 新型儲能電池製造方式 4
1-3 研究動機 7
1-4 研究目的 8
第二章 基礎理論與文獻回顧 8
2-1 奈米點儲能電池操作機制 9
2-1-1 新能階產生機制 9
2-1-2 充電機制 11
2-1-3 放電機制 12
2-2奈米點儲能電池操作原理 14
2-2-1 F-N穿隧效應 (Fowler-Nordheim Tunneling) 14
2-2-2直接穿隧 (Direct tunneling) 16
2-3儲電層的特性理論 17
2-3-1 MOS結構的C-V曲線特性 17
2-3-2 聚積區(Accumulation) 17
2-3-4 反轉區(Inversion) 18
2-3-5 介面電荷對C-V圖的影響 20
2-4 儲電層之電性原理 22
2-5 量子現象 23
2-5-1 量子侷限效應(Quantum Confinement Effect) 23
2-5-2 庫倫阻塞效應(Coulomb Blockade Effect) 23
2-6半導體奈米晶之儲電層製備方式 24
2-7 電漿光譜與薄膜特性之關聯 29
第三章 實驗方法與步驟 32
3-1 奈米點儲能電池之材料與結構 32
3-1-1 Ge奈米點儲能電池元件能帶圖 32
3-2 實驗系統說明 34
3-2-1電漿輔助化學氣相沉積(PECVD)系統 34
3-2-2 高溫爐管 35
3-2-3 直流電漿磁控濺鍍系統[27] 35
3-3實驗流程 36
3-3-1基板清洗 38
3-3-2 製備SiGe薄膜 38
3-3-3 SiGe薄膜-氧氣熱退火處理 38
3-3-4 製備n型半導體層 40
3-3-5 電極沉積-銀電極 40
3-4分析方法 41
3-4-1 拉曼光譜分析儀 (Raman spectrum) 41
3-4-2 n&k薄膜測厚儀 (n&k Analyzer) 42
3-4-3 高解析電子能譜儀 (High resolution X-ray Photoelectron Spectrometer, XPS) 43
3-4-4 光學放射光譜儀 (Optical emission spectroscopy,OES) 46
3-4-5穿透式電子顯微鏡(Transmission electron microscope, TEM) 51
3-4-6 電性量測 (Capacitance-voltage, C-V & Current-voltage, I-V) 51
3-4-7 充放電特性量測 (Charging & Discharging) 52
第四章 實驗結果 53
4-1 SiGe薄膜特性 53
4-1-1 射頻功率之影響 54
4-1-2 GeH4/(GeH4+SiH4)流量比之影響 60
4-1-3 OES-ratio(Ge*/Si*)及XGe與薄膜中Ge含量的關聯分析 65
4-2 不同沉積時間之SiGe薄膜厚度 66
4-2-1 薄膜特性分析 67
4-3 18 nm、75 nm及235 nm SiGe薄膜作為儲電層經相同退火條件的比較: 69
4-3-1電特性分析 69
4-3-2表面影像分析 71
4-4 18 nm SiGe薄膜特性分析 74
4-5 18nm SiGe薄膜作為儲電層經不同退火時間的比較: 76
4-5-1 電特性分析 76
4-6 18nm SiGe薄膜作為儲電層經不同退火溫度的比較: 80
4-6-1 電特性分析 80
4-6-2 儲電層特性分析 83
4-7 18 nm SiGe薄膜上層覆蓋氧化層經熱退火處理: 84
4-7-1 Raman分析 85
4-7-2 電特性分析 86
4-8 n-type layer/charge layer /p-Si substrate結構 89
4-8-1 Ge奈米點儲能電池充放電特性 89
第五章 結論 91
5-1 總結 91
參考文獻 93
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