臺灣博碩士論文加值系統

商業用導電膠已被使用了數十年，在半導體元件COG（Chip on Glass, COG）、COB（Chip on Board, COB）、LCD（Liquid Crystal Display, LCD）模組組裝等應用範圍上，導電膠皆扮演著舉足輕重的地位，如何得到良好導電性的導電膠，填充金屬粒子的種類、幾何形狀、大小及添加比例，稀釋劑種類和比例的應用，以期金屬粒子在高分子膠體中均勻分佈，並減少氣泡的產生，以及適當的烘烤溫度是重要的考量因素。因此，本篇研究分別以不同比例之片狀、樹枝狀及球狀銀、銅粉為填充劑，均勻混和於Epoxy828環氧樹脂中，並添加不同種類之稀釋劑如DPM、BCA、二甲苯以及分散劑，在175℃、190℃與210℃烘烤溫度，試圖找出最佳導電膠製程條件，並利用掃描式電子顯微鏡（SEM）與光學顯微鏡（OM）觀察來比對導電度與製程條件以及顯微組織間之關係。另外，針對片狀銀、銅粉填充劑添加奈米銀、銅粉之影響也同時進行探討。

Conductive adhesives have been commercially available for decades and are widely used in the electronics industry such as COG（Chip on Glass, COG）, COB（Chip on Board, COB）, LCD（Liquid Crystal Display, LCD）modules assembly applications. To get a high performance conductive adhesive electrically, the geometry, size, and percentage of the filled particles are crucial factors. In addition, the applied dilute solvent, eliminating bubbles resulting from preparation processes, and proper curing temperature are also important factors to be considered. In this investigation, various amounts of flake, dendrite and sphere silver powders and copper powders are used as conductive fillers and mixed in an Epoxy 828 resin. DPM, BCA, XYLENE and dispersant are added as dilute solvent to keep filler particles distributed uniformly in the resin. Curing temperatures are set at 175oC, 190oC and 210oC and an optimum condition for processing conductive adhesives is determined. The mechanism of conductivity achievement in conductive adhesives is analyzed by comparing processing conditions, resistivity and microstructures (both OM and SEM observations). Furthermore, the influence of adding nano-sized silver particles and copper particles on the resistivity of the conductive adhesives is also investigated.

總 目 錄
中文摘要.....................................................Ⅰ
英文摘要.....................................................Ⅱ
誌謝.........................................................Ⅲ
總目錄.......................................................IV
圖目錄......................................................VⅡ
表目錄.......................................................XI
第一章 緒論...................................................1
1-1研究背景與動機.............................................1
第二章 原理與文獻回顧.........................................3
2-1導電膠之分類...............................................3
2-1-1以導電形式分類...........................................3
2-1-1-1均向型導電膠 (Isotropic Conductive Adhesive)...........3
2-1-1-2單向型導電膠 (Anisotropic Conductive Adhesive).........3
2-1-2以樹脂操作使用條件分類...................................4
2-1-2-1常溫硬化型導電膠.......................................4
2-1-2-2熱硬化型導電膠.........................................5
2-2導電膠的成分...............................................5
2-2-1黏著劑用基材.............................................6
2-2-1-1環氧樹脂熱硬化之反應機構...............................7
2-2-2導電性填充物.............................................8
2-2-3其他添加劑..............................................10
2-3導電膠的基本性質..........................................11
2-4導電粒子的分散............................................13
2-4-1粒子間靜電力之分散原理（D.L.V.O理論)....................13
2-4-2立體障礙之穩定效果......................................14
2-5導電膠之導電機構..........................................15
2-5-1滲透理論（Percolation Theory)...........................15
2-5-2穿遂效應（Tunnel Effect）...............................22
2-6逐步硬化原理..............................................23
2-7固體粒子在流體中之沉降....................................24
2-8環氧樹脂之熱硬化動態黏度流變行為..........................28
2-9導電膠充填之方法..........................................30
2-9-1網印....................................................30
2-9-2黏度對網印之影響........................................30
2-9-3抗垂流指數（thixotropic index-Ti）之介紹................31
第三章 實驗內容..............................................32
3-1實驗藥品與材料............................................32
3-2儀器與設備................................................35
3-3實驗流程..................................................38
3-4實驗方法..................................................39
3-4-1樹脂系統的配方..........................................39
3-4-2導電膠試片之備置........................................40
3-4-3導電膠填充粒子基本特性量測..............................40
3-4-3-1示差掃描熱量計（DSC）.................................40
3-4-3-2熱重分析儀（TGA）.....................................40
3-4-3-3 X-Ray繞射分析儀（XRD）...............................41
3-4-3-4光學顯微鏡（OM）......................................41
3-4-3-5掃描式電子顯微鏡（SEM）...............................42
3-4-3-6場放射型掃描式電子顯微鏡（FESEM）.....................42
3-4-4導電膠電阻率量測........................................42
3-4-5導電膠動態黏彈觀察......................................45
3-4-6導電膠顯微組織觀察......................................45
3-4-7導電膠導電機構分析......................................46
3-4-8導電膠吸濕性測試分析....................................46
第四章 結果與討論............................................47
4-1導電填充粒子分析..........................................47
4-1-1樹脂系統之DSC分析.......................................47
4-1-2導電填充粒子之DSC觀察...................................48
4-1-3導電填充粒子之TGA觀察...................................50
4-1-4導電填充粒子氧化情形之X-Ray分析及SEM觀察................53
4-2氣泡造成之電性損害........................................62
4-3不同形狀導電填充粒子對導電銀膠之電性分析..................63
4-4不同烘烤溫度對導電銀膠之電性影響..........................68
4-5不同稀釋溶劑對導電銀膠之電性影響..........................68
4-6不同形狀導電填充粒子對導電銅膠之電性分析..................69
4-7添加奈米粉體對導電膠電性之影響............................74
4-8添加分散劑對導電膠粒徑分散與電性之影響....................78
4-9填充不同粒徑銀粉之動態黏彈變化............................79
4-10導電膠吸溼性測試分析.....................................81
第五章 結論..................................................83
第六章 參考文獻..............................................85
第七章 附錄..................................................89
附錄一 片狀銀膠在不同樹脂配方系統、製程條件下之導電情形..89附錄二 樹枝狀銀膠在不同樹脂配方系統、製程條件下之導電情形........91
附錄三 片狀銅膠在不同樹脂配方系統、製程條件下之導電情形......93
附錄四 樹枝狀銅膠在不同樹脂配方系統、製程條件下之導電情形....94
附錄五 球狀銅膠在不同樹脂配方系統、製程條件下之導電情形......95附錄六 封裝信賴性試驗........................................96
圖目錄
圖2-1等方向型導電膠之導電方式.................................3
圖2-2異方向型導電膠之導電方式.................................4
圖2-3環氧樹脂之結構式.........................................7
圖2-4環氧樹脂逐步硬化聚合反應模式.............................8
圖2-5粒子表面之電雙層結構圖..................................14
圖2-6粒子吸附高分子物質形成立體障礙之示意圖..................15
圖2-7 滲透模式示意圖.........................................16
圖2-8導電填充粒子之形狀係數與體積分率之關係圖................21
圖2-9穿遂效應示意圖..........................................22
圖2-10雙烘烤硬化系統之示意圖.................................23
圖2-11拖曳係數表.............................................27
圖2-12環氧樹脂在硬化過程中,典型的黏度變化曲線圖..............29
圖2-13單位流體...............................................30
圖2-14抗垂流體的黏度隨時間之變化關係圖.......................31
圖3-1實驗流程圖..............................................38
圖3-2光學顯微鏡表面及粉體分佈觀察圖..........................42
圖3-3四點探針示意圖..........................................43
圖3-4四點探針之校正因素圖....................................43
圖3-5導電膠膠體與內部氣泡殘留之OM觀察圖......................45
圖3-6導電膠過度烘烤樹脂產生裂解之OM觀察圖....................45
圖3-7導電膠粉體沉降之SEM觀察圖...............................45
圖3-8導電膠粉體凝聚之SEM觀察圖...............................45
圖3-9樹枝狀導電銀膠滲透門檻30％之橫截面SEM觀察圖.............46
圖3-10片狀導電銀膠滲透門檻60％之橫截面SEM觀察圖..............46
圖4-1導電膠樹脂配方之DSC放熱反應分析圖.......................47
圖4-2片狀銀粉之DSC放熱反應分析圖.............................48
圖4-3樹枝狀銀粉之DSC放熱反應分析圖...........................48
圖4-4奈米銀粉之DSC放熱反應分析圖.............................49
圖4-5片狀銅粉之DSC放熱反應分析圖.............................49
圖4-6樹枝狀銅粉之DSC放熱反應分析圖...........................49
圖4-7球狀銅粉之DSC放熱反應分析圖.............................49
圖4-8奈米銅粉之DSC放熱反應分析圖.............................49
圖4-9片狀銀粉之TGA熱重分析圖.................................50
圖4-10樹枝狀銀粉之TGA熱重分析圖..............................51
圖4-11奈米銀粉之TGA熱重分析圖................................51
圖4-12片狀銅粉之TGA熱重分析圖................................51
圖4-13樹枝狀銅粉之TGA熱重分析圖..............................52
圖4-14球狀銅粉之TGA熱重分析圖................................52
圖4-15奈米銅粉之TGA熱重分析圖................................52
圖4-16片狀銀粉XRD結構繞射分析圖..............................54
圖4-17樹枝狀銀粉XRD結構繞射分析圖............................55
圖4-18奈米級銀粉XRD結構繞射分析圖............................55
圖4-19片狀銅粉XRD結構繞射分析圖..............................56
圖4-20樹枝狀銅粉XRD結構繞射分析圖............................56
圖4-21球狀銅粉XRD結構繞射分析圖..............................57
圖4-22奈米級銅粉XRD結構繞射分析圖............................57
圖4-23片狀銀粉模擬高溫烘烤產生失效氧化之SEM外觀分析..........58
圖4-24樹枝狀銀粉模擬高溫烘烤產生失效氧化之SEM外觀分析........58
圖4-25奈米銀粉模擬高溫烘烤產生失效氧化之SEM外觀分析..........59
圖4-26片狀銅粉模擬高溫烘烤產生失效氧化之SEM外觀分析..........59
圖4-27樹枝狀銅粉模擬高溫烘烤產生失效氧化之SEM外觀分析........60
圖4-28球狀銅粉模擬高溫烘烤產生失效氧化之SEM外觀分析..........60
圖4-29奈米銅粉模擬高溫烘烤產生失效氧化之SEM外觀分析..........61
圖4-30導電膠在真空作業前後之金相觀察圖.......................62
圖4-31實施真空處理與未實施真空處理之導電膠電阻率圖...........62
圖4-32片狀銀粉添加稀釋溶劑在不同烘烤時間下之導電膠電阻率圖...64
圖4-33樹枝狀銀粉添加稀釋溶劑在不同烘烤時間下之導電膠電阻率圖.65
圖4-34片狀導電銀膠之SEM橫截面觀察圖..........................66
圖4-35樹枝狀導電銀膠之SEM橫截面觀察圖........................67
圖4-36不同外觀形狀填充粒子之導電銅膠導電率圖.................69
圖4-37片狀導電銅膠之SEM橫截面觀察圖..........................70
圖4-38樹枝狀導電銅膠之SEM橫截面觀察圖........................71
圖4-39球狀導電銅膠之SEM橫截面觀察圖..........................71
圖4-40球狀銅粉摻混樹枝狀銅粉之導電膠導電率圖.................72
圖4-41球狀混合樹枝狀導電銅膠之SEM橫截面觀察圖................73
圖4-42片狀銀粉、奈米銀粉之導電膠導電率圖.....................74
圖4-43片狀銅粉、奈米銅粉之導電膠導電率圖.....................75
圖4-44奈米銀粉在片狀銀粉導電膠中分散情形之FESEM觀察圖........76
圖4-45奈米銀粉充填於片狀銀粉導電膠間隙之FESEM觀察圖..........76
圖4-46奈米銅粉在片狀銅粉導電膠中分散情形之FESEM觀察圖........77
圖4-47奈米銅粉充填於片狀銅粉導電膠間隙之FESEM觀察圖..........77
圖4-48球狀銅粉添加分散劑後之導電率變化圖.....................78
圖4-49球狀銅粉添加分散劑之SEM橫截面觀察圖....................79
圖4-50片狀銀粉添加分散劑之SEM橫截面觀察圖....................79
圖4-51不同粒徑銀粉導電膠之熱硬化動態黏彈變化.................80
圖4-52不同粒徑銀粉導電膠之熱硬化動態黏彈變化.................80
圖4-53不同填充粉體粒徑導電膠吸濕性之影響圖...................81
表目錄
表2-1電子封裝用樹脂之性能比較表...............................6
表2-2部分導電金屬之導電性質表................................10
表2-3部分導電金屬之還原電位表................................10
表2-4以Site Percolation所計算的臨界參考數值表................17
表2-5以Bond Percolation所計算的臨界參考數值表................19
表3-1實驗樹脂配方表..........................................39
表3-2矩形薄膜側面修正係數表..................................44
表3-3薄膜厚度修正係數表......................................44
表4-1導電填充粒子規格表......................................54
表4-2封裝元件吸濕測試控制層級/JEDEC試驗方法與規範標準........82

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