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姓名 林思旻(Ssu-Min Lin) 查詢紙本館藏 畢業系所 能源工程研究所 論文名稱 水解二乙基鋅於近耦合噴淋式反對稱腔體 之MOCVD模擬設計分析
(Simulation design and analysis of diethylzinc hydrolysis in an anti-symmetric close coupled showerhead MOCVD reactor)相關論文 檔案 [Endnote RIS 格式]
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摘要(中) 對於多晶氧化鋅(ZnO)其本身電阻值高，因此一般於透明導電薄膜的應用上，則會將其摻雜?族元素（硼、鋁、鎵、銦等），使其導電特性提高，同時也增加其高溫穩定性。而在單晶氧化鋅(ZnO)是一種N型Ⅱ-Ⅵ族寬帶隙半導體材料，於可見光範圍內具有高穿透率，因為擁有與GaN相類似的特性，且激子束縛能高於GaN，有望取代GaN成為做紫外光LD和LED的材料。
本研究針對MOCVD近耦合噴淋式反對稱腔體進行熱場、流場及物種傳輸模擬研究。起初，依照生長ZnO薄膜的化學反應式，建立表面吸附模型，比較不同吸附物種與化學反應式對於ZnO薄膜生長效率之影響，將10條氣相化學反應式簡化為3條主要化學反應式。
本腔體的設計中，考量透明導電膜為方形，因此針對方形薄膜設計方形反應腔體，而大型玻璃載盤轉動困難，以反對稱進氣孔交錯的方式來達到物種沉積均勻的效果。同時探討改變製程參數對表面吸附效率與薄膜生長變化率之影響，ZnO薄膜生長效率會隨著製程壓力增加而升高，隨著溫度改變的生長率當壓力增大斜率也越大，另外，ZnO薄膜生長效率，隨著壓力改變的生長率當製程溫度增大斜率也越大，流量增加時，ZnO薄膜生長效率會提高，但流量到達一定的倍數並不會增加長率，進氣孔徑擴大，生長效率會提高，但孔徑到達一定的數值並不會提升生長效率，本研究將三個抽氣孔半徑於設定範圍內參數掃描，以便達到ZnO薄膜生長變化率最小值，模擬研究結果為上方抽氣孔20mm、中間抽氣孔35mm與下方抽氣孔25mm會有最低的生長變化率為0.0802%。摘要(英) polycrystalline zinc oxide has a high resistance value, so generally, in the application of a transparent conductive film, it is doped with ? elements (boron, aluminum, gallium, indium, etc.) to improve its conductivity and also improve its conductivity. Increase its high temperature stability.However, Single crystal zinc oxide (ZnO) is an N-type II-VI wide band gap semiconductor material with high transmittance in the visible range. It has similar properties to GaN and exciton binding energy is higher than GaN. Substituting GaN has become a material for UV LDs and LEDs .
In this study, the thermal field, flow field and species transfer simulation of MOCVD near-coupled spray-type anti-symmetric cavity were studied. At first, according to the chemical reaction formula of the grown ZnO thin film, a surface adsorption model was established to compare the effects of different adsorbed species and chemical reaction formulas on the growth efficiency of ZnO thin films. Ten gas phase chemical reaction schemes were simplified into three main chemical reaction formulas.
In the design of the cavity, the transparent conductive film is considered to be square. Therefore, a square reaction cavity is designed for the square film, and the large glass carrier is difficult to rotate, and the effect of uniform deposition of the species is achieved by opposing the staggered inlet holes. At the same time, the effect of changing process parameters on surface adsorption efficiency and film uniformity is discussed. The growth efficiency of ZnO thin film increases with the increase of process pressure. The growth rate increases with temperature and the slope increases with pressure. In addition, ZnO thin film growth efficiency, growth rate with pressure change When the process temperature increases, the slope increases; the flow rate increases, the growth efficiency of ZnO thin film increases, but the flow rate reaches a certain multiple does not increase the long rate; the inlet pore size increases, and the growth efficiency will increase, but the aperture reaches a certain value does not improve the growth efficiency. In this study, the parameters of the three venting radii within the set range are scanned to achieve the minimum error of the ZnO film uniformity. The simulation result is 20mm above the hole. The lowest uniformity error of the upper uniform hole 20mm, the middle suction hole 35mm and the lower suction hole 25mm will have the lowest uniformity error of 0.0802%.關鍵字(中) ★ ZnO
★ MOCVD
★ 近耦合噴淋式腔體關鍵字(英) ★ ZnO
★ MOCVD
★ showerhead論文目次 目錄
摘要 I
Abstract II
目錄 IV
圖目錄 VII
表目錄 X
符號說明 XI
第一章 緒論 1
1-1研究背景 1
1-2 MOCVD薄膜沉積過程 2
1-2-1 氣相反應過程 2
1-2-2 吸附過程 2
1-2-3 薄膜表面沉積過程 4
1-3 MOCVD反應腔體中的傳輸現象 5
1-3-1 高速載盤旋轉式腔體 5
1-3-2近耦合噴淋式腔體 5
1-3-3水平式腔體中的傳輸現象 6
1-3-4 垂直式腔體中的傳輸現象 6
1-3-5行星式反應腔體 6
1-4 文獻回顧 8
1-5研究動機與目的 9
第二章 研究方法 19
2-1物理系統 19
2-1-1無因次參數 19
2-1-2 基本假設 21
2-1-3 統御方程式 22
2-1-4 邊界條件 24
2-2化學反應方程式 25
2-2-1 氣相化學反應 25
2-3混合氣體物理參數 27
2-4化學反應路徑 29
2-4-1氣相反應 (Gas phase reactions) 29
2-5表面化學計算 30
2-5-1 吸附反應 (Adsorption reaction) 30
2-6薄膜沉積速率 32
第三章 數值方法 37
3-1 數值求解步驟 37
3-2 網格配置測試 37
3-3 收斂公差測試 37
第四章 結果與討論 40
4-1穩態模型驗證與反應式簡化探討 40
4-1-1 模型對比驗證 40
4-1-2 不同反應式對於濃度分布之影響 40
4-2基本製程參數之探討 41
4-2-1反應腔體壓力與基板溫度之影響 41
4-2-2反應進氣流量之影響 41
4-3反應腔體幾何參數之探討 42
4-3-1 改變進氣孔徑之影響 42
4-3-2改變進氣孔位置之影響 42
4-3-3 改變進氣孔數量之影響 42
4-3-4改變抽氣孔徑之影響 43
4-3-4抽氣孔徑參數掃描 43
第五章 結論與未來研究方向 77
5-1 結論 77
5-2 未來研究方向 78
參考文獻 79
圖目錄
圖1-1 化學氣相沉積反應步驟[3] 10
圖1-2 化學吸附與物理吸附能量示意圖[4] 10
圖1-3 物理吸附作用力[7] 11
圖1-4薄膜表面沉積步驟[8] 11
圖1-5高速載盤旋轉式腔體圖[9] 12
圖1-6近耦合噴淋式腔體圖[10] 12
圖1-7 水平式反應腔體圖[11] 13
圖1-8 垂直式反應腔體圖[12] 13
圖1-9 行星式反應腔體圖[13] 14
圖1-10 參雜硼之ZnO的沉積效率隨沉積溫度變化圖[14] 14
圖1-11 參雜硼之ZnO的電特性隨沉積溫度變化圖[14] 15
圖1-12 H型垂直反應腔體(a)3維結構與晶圓表面分布(b)2維流向示意圖[15] 16
圖1-13 二乙基鋅水解反應路徑示意圖[16] 17
圖1-14 ZnO的生長效率隨溫度變化圖[16] 17
圖1-15 反應流程示意圖[17] 18
圖1-16 ZnO薄膜生長效率於不同壓力下隨基板溫度變化圖[17] 18
圖2-1 反應腔體示意圖 33
圖2-2 玻璃載盤示意圖 33
圖2-2 入口交錯分布示意圖(深藍色為H2O、亮色為DEZn) 34
圖2-3 氣相化學反應式[15] 35
圖2-4 表面化學反應式[15] 35
圖3-1 數值求解步驟 38
圖3-2反應腔體網格示意圖 38
圖3-3 網格測試圖 39
圖3-4 網格收斂性測試 39
圖4-1 反應腔體模型 44
圖4-2 文獻之ZnO薄膜生長效率與COMSOL模擬對比 44
圖4-3 全化學反應式之物種最終濃度圖 45
圖4-4 4~6條化學反應式之物種最終濃度圖 45
圖4-5 6條氣相化學反應式之物種最終濃度圖 46
圖4-6 6條反應式中4~6條化學反應式之物種最終濃度圖 46
圖4-7 3條氣相化學反應式之物種最終濃度圖 47
圖4-8 預因子A大於108之最終濃度圖 47
圖4-9 不同壓力隨溫度變化之ZnO薄膜生長率比較圖 48
圖4-11 (固定載氣Ar流量)改變反應物流量隨溫度變化之ZnO薄膜生長率圖 49
圖4-12 不同進氣孔徑隨溫度變化之ZnO薄膜生長率比較圖 49
圖4-13 抽氣孔為三大圓ZnO薄膜生長率等位線圖(nm/h) 50
圖4-14 抽氣孔為三大圓之流線圖(Zn(CH2CH3)2H2O之莫耳分率) 50
圖4-15 於z=0之玻璃載盤表面切線示意圖(a)x=0.2m(b)y=0.1m 51
圖4-16 抽氣孔為三大圓於x=0.2m切線上之ZnO薄膜生長率(nm/h) 52
圖4-17 抽氣孔為三大圓於y=0.1m切線上之ZnO薄膜生長率(nm/h) 52
圖4-18 抽氣孔為上小圓ZnO薄膜生長率等位線圖(nm/h) 53
圖4-19 抽氣孔為上小圓之流線圖 53
圖4-20 抽氣孔為上小圓於x=0.2m切線上之ZnO薄膜生長率(nm/h) 54
圖4-21 抽氣孔為上小圓於y=0.1m切線上之ZnO薄膜生長率(nm/h) 54
圖4-22 進氣孔位移前後示意圖 55
圖4-23 位移進氣孔後ZnO薄膜生長率(nm/h) 55
圖4-24 於x=0.2m切線上之位移進氣孔後ZnO薄膜生長率(nm/h) 56
圖4-25 y=0.1m切線上之位移進氣孔後ZnO薄膜生長率(nm/h) 56
圖4-26 增加y方向進氣孔數量後ZnO薄膜生長率(nm/h) 57
圖4-27 增加y方向進氣孔數量後之流線圖(Zn(CH2CH3)2H2O之莫耳分率) 57
圖4-28 增加x方向進氣孔數量後ZnO薄膜生長率(nm/h) 58
圖4-29 增加x方向進氣孔數量後之流線圖(Zn(CH2CH3)2H2O之莫耳分率) 58
圖4-30 同時增加x方向與y方向進氣孔數量後ZnO薄膜生長率(nm/h) 59
圖4-31 同時增加x與y方向進氣孔數量後之流線圖(Zn(CH2CH3)2H2O之莫耳分率) 59
圖4-32 抽氣孔徑改為三大圓之ZnO薄膜生長率(nm/h) 60
圖4-33 抽氣孔徑改為三大圓之流線圖(Zn(CH2CH3)2H2O之莫耳分率) 60
圖4-34 於x=0.2m切線上之抽氣孔徑改為三大圓ZnO薄膜生長率(nm/h) 61
圖4-35 於y=0.1m切線上之抽氣孔徑改為三大圓ZnO薄膜生長率(nm/h) 61
圖4-36 抽氣孔徑改為中小圓之ZnO薄膜生長率(nm/h) 62
圖4-37 抽氣孔徑改為中小圓之流線圖(Zn(CH2CH3)2H2O之莫耳分率) 62
圖4-38 抽氣孔徑改為下小圓之ZnO薄膜生長率(nm/h) 63
圖4-39 抽氣孔徑改為下小圓之流線圖(Zn(CH2CH3)2H2O之莫耳分率) 63
圖4-40 抽氣孔徑改為三小圓之ZnO薄膜生長率(nm/h) 64
圖4-41 抽氣孔徑改為三小圓之流線圖(Zn(CH2CH3)2H2O之莫耳分率) 64
圖4-42 於x=0.2m切線上之抽氣孔徑改為三小圓ZnO薄膜生長率(nm/h) 65
圖4-43 於y=0.1m切線上之抽氣孔徑改為三小圓ZnO薄膜生長率(nm/h) 65
圖4-44於x=0.2m切線上ZnO薄膜生長變化率低於0.1%之幾何參數(nm/h) 66
圖4-45於y=0.1m切線上ZnO薄膜生長變化率低於0.1%之幾何參數(nm/h) 66
圖4-46 最佳幾何參數之ZnO薄膜生長率(nm/h)(x1,x2,x3)=(20,35,25)mm 67
圖4-47 最佳幾何參數之流線圖(Zn(CH2CH3)2H2O之莫耳分率) 67
圖4-48 物種Zn(CH2CH3)2H2O濃度分布圖(z =0切面) 68
圖4-49 物種Zn(CH2CH3)OH濃度分布於玻璃載圖(z =0切面) 68
圖4-50 於x=0.2m切線上之最佳幾何參數ZnO薄膜生長率(nm/h) 69
圖4-51 於y=0.1m切線上之最佳幾何參數ZnO薄膜生長率(nm/h) 69
表目錄
表2-1 Lennard - Jones parameters[25-29] 36
表2-2 主要氣相化學反應式 36
表2-2 主要表面化學反應式 36
表4-1 ZnO薄膜生長率誤差生長變化率 70
表4-2 改變三個抽氣孔半徑之參數掃描結果 71參考文獻 [1] CIGS薄膜太陽能電池, moneydj
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