電子產品是現代人日常生活中不可或缺的一部分，而不論電子產品功能為何，都需要導體來傳遞電流，。一般來說金、銀、銅是最常見的導電油墨印刷材料，前兩者具有良好的化學穩定性和低電阻率(金電阻率為2.4 μΩ·cm，而銀是1.59 μΩ·cm)，但金作為油墨成本過高，因此在市面上的導電油墨的主要材料都以銀為主，但銀的價格仍是過高，銅因其價格低廉(約為銀價格1/7)和其優異導電性(1.7 μΩ·cm)，所以近年來銅逐漸成為可以替代銀成為導電油墨的材料，但銅在經過奈米化後，容易於空氣中氧化且容易聚集，所以油墨的製備、分散性、保存是奈米銅油墨最需要去克服的地方。本研究，以環保的抗壞血酸合成奈米銅顆粒並選用適當的保護劑及介面活性劑，藉由調整實驗參數合成抗氧化的奈米銅顆粒，並配製成導電油墨。以不同塗佈技術製及不同燒結的方式製備導電銅膜，並藉由添加黏著劑使附著力達到4B，硬度達到H，片電阻可達到< 0.6 Ω/□，另外藉由塗佈機制備導電圖騰，線寬為0.1 cm，電阻可達到5 Ω，油墨存放可維持至少半年不被氧化，燒結後的銅膜可維持至少5個月的低片電阻。

In this study, we focus on how to deploy a anti-oxidized nano copper conductive ink. Copper nanoparticles were synthesized with environmentally-friendly ascorbic acid and appropriate protective agents and surfactant were selected. The anti-oxidized nano copper particles were synthesized by adjusting experimental parameters and formulated into conductive inks. The conductive copper film is prepared by different coating techniques and different sintering methods, and the adhesion is up to 4B by adding an adhesive, the hardness reaches H, the sheet resistance can reach <0.6 Ω/□, and the conductive is prepared by a coater. The totem has a line width of 0.1 cm and a resistance of 5 Ω. The ink can be stored for half a year without oxidation. The sintered copper film can maintain a low sheet resistance of nearly 5 months.

目錄
一、	緒論	1
1-1	前言	1
1-2	研究動機與目的	2
二、	原理及文獻回顧	3
2-1	簡介	3
2-1-1	奈米材料	3
2-1-2	導電油墨	4
2-2	奈米銅顆粒簡介	6
2-2-1	製備方法	6
2-2-2	抗氧化方式	11
2-3	奈米銅顆粒特性	19
2-3-1	表面電漿共振	19
2-3-2	奈米銅顆粒懸浮原理	21
2-4	奈米銅顆粒燒結	29
三、	實驗方法	32
3.1	實驗流程與架構	32
3.2	實驗藥品	34
3.3	實驗儀器	39
3.4	實驗步驟	44
3-4-1	化學合成法合成奈米銅顆粒	44
3-4-2	奈米銅油墨配製	47
3-4-3	導電薄膜製備	48
3-4-4	導電圖騰製備	51
3.5	結構分析與性質測試	52
3-5-1	形態分析 (SEM、TEM、OM)	52
3-5-2	結晶構造分析	52
3-5-3	性質分析	53
四、	結果與討論	60
4-1	奈米銅顆粒性質和結構分析	60
4-1-1	反應溶劑種類	60
4-1-2	反應參數	62
4-1-3	銅顆粒晶體分析	65
4-1-4	PVP保護劑的作用	67
4-1-5	銅顆粒熔點	70
4-1-6	溶液中顆粒大小	70
4-1-7	油墨穩定性	71
4-1-8	油墨配方	72
4-2	銅膜性質分析	73
4-2-1	燒結參數	73
4-2-2	塗佈方法	77
4-2-3	黏著劑	79
4-2-4	可撓性	88
4-2-5	附著力測試	90
4-2-6	硬度測試(Pencil hardness)	93
4-2-7	親疏水測試 (Contact angle)	95
4-2-8	脈衝光燒結(Sintering by intense pulsed light, IPL)	97
4-2-9	銅膜穩定性	102
4-3	應用	106
4-3-1	點膠機	106
4-3-2	噴塗機	106
五、	結論	109
六、	參考文獻	110
七、	附錄	117

 
圖目錄
圖2-1 奈米科技於日常生活中例子(a)彩蝶效應[3]、(b)蓮花效應[4]	3
圖2-2 導電線路製作，(a)傳統曝光顯影、(b)直接印刷成型[7]	5
圖2-3 反應驅動力與平均粒徑的關係(最大反應驅動力)[13]	9
圖2-4 抗壞血酸還原銅顆粒，(a) pH值3.0、(b) pH值6.5 [16]	10
圖2-5 由無定形碳包附的銅顆粒[18]	11
圖2-6 (a)具有3nm厚石墨烯層的銅顆粒的TEM圖像(左)和示意圖(右)、	12
(b)熱重分析（TGA）證實這些顆粒的熱穩定性高達165 oC [21]	12
圖2-7 (a)未塗覆的Cu NPs的XRD圖案、(b)Cu / SiO2奈米顆粒、	13
(c)製備後一個月的Cu / SiO2 NPs，●：Cu、▲：Cu2O [22]	13
圖2-8 單個銅顆粒的合成且透過金屬轉移反應形成銀殼的示意圖[26]	14
圖2-9 (a) 銅-銀(核-殼)的TEM圖、(b) 銅-銀(核-殼)的SEM圖、	14
(c) 在空氣氣氛下的銅-銀(核-殼)的TGA [26]	14
圖2-10 硫醇包覆奈米銅顆粒示意圖[28]	15
圖2-11 各種不同分子量PVP製備銅顆經不同溫度處理之電阻率變化[31]	16
圖2-12 PVP包覆銅顆粒示意圖[33]	16
圖2-13 SDS與PVP包覆銅顆粒示意圖，(a) 由PVP絮凝誘導的顆粒聚集、	17
(b)由PVP的鏈延伸誘導的顆粒分散[34]	17
圖2-14 CTAB和PVP包覆銅顆粒示意圖[35]	18
圖2-15 羧酸預處理銅顆粒[2]	19
圖2-16 導電薄膜電阻率變化(a) 5分鐘(b) 30分鐘(c) 60分鐘[37]	19
(u-Cu NPs:未用甲酸預處理、f-CuNPs: 甲酸預處理)	19
圖2-17 表面電漿共振[38]	20
圖2-18 銅立方顆粒與其SPR特徵峰[33]	21
圖2-19 不同SDS濃度形成不同尺寸奈米銅顆粒的SPR圖[43]	21
圖2-20 DLVO理論圖[44]	22
圖2-21 膠體雙電層示意圖	24
圖2-22 具有雙電層兩膠體之間的相互作用可看成由彈簧連接的兩個塊體[45]	25
圖2-23立體障礙，(a) 滲透壓效應、(b) 空間限制效應[45]	27
圖2-24 (a) 膠體的空間穩定性(Steric stabilization of colloids)、(b) 膠體的涸竭穩定效應 (Depletion stabilization of colloids)[45]	28
圖2-25 可以降低粒子能量的兩種可能途徑的示意圖[51]，(a) 緻密化，然後是晶粒生長、(b) 粒子粗化，以較小的顆粒為代價而生長	29
圖2-26 燒結原子的質傳機制[51]	30
圖3-1 實驗流程架構	33
圖3-2 銅顆粒合成裝置示意圖	45
圖3-3  合成奈米銅顆粒的實驗流程	46
圖3-4 反應試瓶溶液之顏色變化，(a) PVP +CuSO4+ DEG、	46
(b) PVP +CuSO4+ AA +DEG、(c)第一次離心上層液、(d) 第二次離心上層液	46
圖3-5 銅油墨配製流程圖	47
圖3-6 導電銅油墨之塗佈方法	49
(a) Drop coating、(b) Spray coating、(c) Doctor blade	49
圖3-7 高溫爐燒結參數	50
圖3-8 (a) IPL設備圖、(b)燈箱光照示意圖	50
圖3-9 點膠機示意圖	51
圖3-10 噴塗機設備圖	51
圖3-11 四點探針示意圖	55
圖3-12 四點探針校正因數CF [54] d為試片寬度，s為四點探針間距，w為薄膜厚度，a為試片長度	55
圖3-13 四點探針測量位置	56
圖3-14 Classification of adhesion test results (ASTM D 3359-95)	57
圖3-15 鉛筆式硬度計示意圖	58
圖3-16 親疏水示意圖	59
圖4-1 不同溶劑合成銅顆粒之SEM圖，(a)乙二醇、(b)二甘醇，	60
CuSO4/PVP/AA = 1/5/3，反應溫度90 oC，反應時間20分鐘	60
圖4-2 不同反應時間合成銅顆粒之SEM圖，(a) 20分鐘、(b) 60分鐘，	62
溶劑為DEG，反應溫度90 oC	62
圖4-3 不同溫度下合成出之銅顆粒之TEM圖，(a)、(b) 90 oC，(c)、(d) 120 oC，(e)、(f) 140 oC，CuSO4/PVP/AA = 1/5/3，溶劑為DEG，反應時間60 min	63
圖4-4 銅顆粒的紫外光可見光光譜圖，CuSO4/PVP/AA = 1/5/3	64
溶劑DEG，反應溫度90oC，反應時間60分鐘	64
圖4-5剛合成出銅顆粒時的XRD圖	65
合成條件：溶劑為DEG，反應溫度90 oC，反應時間60分鐘	65
CuSO4/PVP/AA：1 / 5 / 3	65
圖4-6氧化亞銅的XRD圖[61]	66
圖4-7氧化銅的XRD圖[62]	66
圖4-8  PVP (Mw 4×104) 的熱重損失圖	68
圖4-9 通過改變CuSO4和PVP之間的莫耳比製備奈米顆粒的SEM，	68
(a) CuSO4 / PVP= 1/3、(b) CuSO4 / PVP= 1/6、(c) CuSO4 / PVP= 1/9 [33]	68
圖4-10 銅顆粒的EDS line scan	69
圖4-11  PVP、銅顆粒、燒結後的銅膜的FTIR圖	69
圖4-12 製備出的奈米銅顆粒DSC圖，CuSO4/PVP/AA= 1 / 5 / 3，	70
溶劑為DEG，反應溫度90 oC，反應時間60分鐘	70
圖4-13 銅顆粒分散於乙醇中的粒徑分佈	71
圖4-14 奈米銅顆粒保存於無水乙醇中的外貌，(a)合成當天，(b)半年後	71
圖4-15 合成出的奈米銅放置半年後XRD圖	72
圖4-16 不同溶劑之銅膜外觀	73
圖4-17 箱型高溫爐中的燒結參數	74
圖4-18 箱型高溫爐燒結出之銅膜外觀，銅油墨CuNP/EtOH(5 wt%)，(a) A-1銅膜 (250 oC, 30 min)、(b) A-2銅膜(200 oC, 30 min)、(c) A-3銅膜(200 oC, 60 min)	75
圖4-19 銅顆粒與銅膜的XRD圖(▲) Cu,(■) Cu2O，(a)合成出之奈米銅顆粒、(b)A-1銅膜(250 oC, 30 min)、(c)A-2銅膜(200 oC, 30 min)、	75
(d)A-3銅膜(200 oC, 60 min)	75
圖4-20 管式高溫爐燒結條件	76
圖4-21 (a) B1銅膜：CuNP/EtOH(10 wt%)油墨未預乾直接放入管式高溫爐燒結 (250 oC, 30 min)、(b) B2銅膜：CuNP/EtOH(10 wt%)油墨先以熱板去除溶劑(65oC)再放入管式高溫爐中燒結 (250 oC, 30 min)	77
圖4-22 添加環氧樹脂之銅膜，(a) 5 wt% DEGBA、(b) 1 wt% DEGBA	80
圖4-23 不同油墨配方之銅膜外觀 (Sintering：250 oC, 30 min)，(a)未添加黏著劑之銅油墨(CuNP/EtOH= 10 wt%)燒結成膜、(b)銅油墨(CuNP/EtOH= 10 wt%，含0.2 wt% PVB)燒結成膜	81
圖4-24 銅膜表面的OM圖(Sintering：250 oC, 30 min)，(a) 未添加黏著劑油墨(CuNP/EtOH= 10 wt%)，倍率100、(b) 未添加黏著劑油墨(CuNP/EtOH= 10 wt%)，倍率500、(c) 添加黏著劑油墨(CuNP/EtOH= 10 wt%，含0.2 wt% PVB)，倍率100、(d) 添加黏著劑油墨(CuNP/EtOH= 10 wt%，含0.2 wt% PVB)，倍率500	82
圖4-25 添加PVB之銅油墨(CuNP/EtOH= 10 wt%，含0.2~5 wt% PVB)靜置7天後產生之沉澱物，(a)無黏著劑、(b)有黏著劑、(c)各濃度黏著劑	84
圖4-26 銅油墨(CuNP/EtOH= 10 wt%)中添加1 wt%介面活性劑，不同靜置天數穩定情形，(a)油墨靜置第1天、(b) 油墨靜置第7天、(c) 油墨靜置第14天	85
圖4-27 油墨(CuNP/EtOH= 10 wt%)添加1 wt%介面活性劑經燒結之銅膜(Sintering：250 oC, 30 min)在不同存放天數之銅膜外觀	86
圖4-28 銅油墨(CuNP/EtOH= 10 wt%)添加0.1 wt%介面活性劑及0.2 wt%黏著劑(PVB, B08-SY)經燒結之銅膜外觀(Sintering：250 oC, 30 min)	87
圖4-29 不同體積的銅油墨(CuNP/EtOH= 10 wt%)滴塗於PI基板上經燒結後銅膜外觀(無黏著劑)，(a)體積0.30 mL、(b)體積0.15 mL	89
圖4-30 添加不同型號黏著劑(0.2 wt%)的銅油墨(CuNP/EtOH= 10 wt%)滴塗於PI基板上經燒結後銅膜外觀	89
圖4-31銅油墨(CuNP/EtOH= 10 wt%)中有無添加黏著劑(0.2 wt%, B08-SY)燒結於不同基板成膜之附著性測試銅膜外觀	91
圖4-32銅油墨(CuNP/EtOH= 10 wt%, Triton-X 100 0.1 wt%)中有無添加黏著劑(0.2 wt%, B08-SY)燒結於不同基板成膜之附著性測試銅膜OM圖	92
(a)With binder / Glass substrate、(b)Without binder / Glass substrate、	92
(c)With binder / PI substrate、(d)Without binder / PI substrate	92
圖4-33 銅油墨(CuNP/EtOH= 10 wt%)中有無添加黏著劑(0.2 wt%, B08-SY)燒結於成膜之硬度測試外觀(a)Without binder、(b)With binder	93
圖4-34銅油墨(CuNP/EtOH= 10 wt%)中有無添加黏著劑(0.2 wt%, B08-SY)燒結於成膜之硬度測試外觀OM圖，(a)未添加黏著劑，HB、(b) 未添加黏著劑H、(c) 添加黏著劑，H、(d) 添加黏著劑，2H	94
圖4-35 基材與不同油墨組成製備出的導電銅膜與水的接觸角，(a) glass slide、(b) PI、(c) 10 wt% Cu / EtOH、(d) 10 wt% Cu / 0.2 wt% PVB / EtOH、(e) 10 wt% Cu /  0.2 wt% PVB / 0.1 wt% Triton X-100 / EtOH、(f) 10 wt%  Cu / 0.2 wt% PVB / 0.1 wt% Tween 20 / EtOH(Sintering：250 oC, 30 min)	96
圖4-36 脈衝光機台Xenon X-1100之光譜	98
圖4-37不同油墨配方經不同能量IPL燒結之銅膜外觀	99
圖4-38 兩種不同燒結方式之銅膜外觀，(a)高溫燒結、(b)IPL燒結	101
圖4-39 兩種不同燒結方式之銅膜SEM圖，(a)高溫燒結、(b)IPL燒結	101
圖4-40 未添加黏著劑銅油墨(CuNP/EtOH= 10 wt%)燒結成膜之存放時間對銅膜片電阻的變化	102
圖4-41添加黏著劑(0.2%, B03-HX)銅油墨(CuNP/EtOH= 10 wt%)經燒結成膜後之存放時間對銅膜片電阻的變化	103
圖4-42添加黏著劑(0.2%, B08-SY)銅油墨(CuNP/EtOH= 10 wt%)經燒結成膜後之存放時間對銅膜片電阻的變化	103
圖4-43不同油墨(CuNP/EtOH= 10 wt%)配方燒結成膜之外觀，(a) 銅油墨未添加黏著劑、(b) 銅油墨添加黏著劑(0.2%, B03-HX)、(c) 銅油墨添加黏著劑(0.2%, B08-SY) (Sintering：250 oC, 30 min)	104
圖4-44不同油墨配方燒結成膜之OM圖，(a) 銅油墨未添加黏著劑、(b) 銅油墨添加黏著劑(0.2%, B03-HX)、(c) 銅油墨添加黏著劑(0.2%, B08-SY)	105
圖4-45 圖騰示意圖	106
圖4-46 3D列印印製遮罩圖	107
圖4-47 噴圖成品示意圖	108
圖4-48 導電圖騰OM圖	108
圖7-1 不同分子量PVP合成銅顆粒	117
圖7-2 分子量55000 PVP合成銅顆粒開始氧化	118
圖7-3 乾燥銅顆粒EDS圖	119
圖7-4 高溫爐燒結銅顆粒EDS圖	120
圖7-5 IPL燒結銅顆粒EDS圖	121

目錄
表2-1 金屬奈米化後熔點變化[5]	4
表2-2 銅顆粒之粒徑與各項特性關係[6]	4
表2-3 金屬材料比較(2019/06)	6
表2-4 Zeta電位大小與膠體穩定性對照表[48、49]	26
表2-5 在燒結的初始階段物質傳輸的路徑[51]	31
表3-1 合成奈米銅顆粒之反應條件	45
表4-1 不同溶劑合成出的銅顆粒粒徑大小的文獻回顧	61
表4-2 銅顆粒SPR文獻回顧	64
表4-3 不同溶劑做為油墨之片電阻	73
表4-4 箱型高溫爐燒結出之銅膜片電阻	75
表4-5 管式高溫爐燒結之銅膜片電阻，B1銅膜：油墨未預乾直接放入管式高溫爐燒結(250 oC, 30 min)、(b) B2銅膜：油墨先以熱板去除溶劑 (65oC)再放入管式高溫爐中燒結(250 oC, 30 min)	77
表4-6 滴塗法製備之銅膜片電阻 (Sintering：250 oC, 30 min)	78
表4-7 刮刀法製備之銅膜片電阻 (Sintering：250 oC, 30 min)	79
表4-8 噴塗法製備之銅膜片電阻 (Sintering：250 oC, 30 min)	79
表4-9 添加環氧樹脂之油墨經燒結後之銅膜片電阻 (Sintering：250 oC, 30 min)	80
表4-10 添加PVB油墨經燒結後之片電阻 (Sintering：250 oC, 30 min)	81
表4-11 添加黏著劑之油墨(CuNP/EtOH= 10 wt%，含0.2 wt% PVB)在不同時間儲存後而製備出之銅膜片電阻比較 (Sintering：250 oC, 30 min)	84
表4-12 油墨(CuNP/EtOH= 10 wt%)添加1 wt%介面活性劑經燒結後銅膜(Sintering：250 oC, 30 min)在不同存放天數之銅膜片電阻	86
表4-13 銅油墨(CuNP/EtOH= 10 wt%)添加0.1 wt%介面活性劑及0.2 wt%黏著劑(PVB, B08-SY)經燒結之銅膜之片電阻(Sintering：250 oC, 30 min)	87
表4-14 銅油墨(CuNP/EtOH= 10 wt%)添加0.2 wt%黏著劑(PVB, B08-SY)及不同濃度Triton X-100銅膜經燒結後之片電阻比較(Sintering：250 oC, 30 min)	88
表4-15 不同體積的銅油墨滴塗於PI基板上經燒結後銅膜之片電阻	89
表4-16 添加不同型號黏著劑(0.2 wt%)的銅油墨(CuNP/EtOH= 10 wt%)滴塗於PI基板經燒結後的銅膜片電阻	90
表4-17 銅油墨中有無添加黏著劑(0.2 wt%, B08-SY)燒結於不同基板成膜之附著性測試結果	92
表4-18 銅油墨中有無添加黏著劑(0.2 wt%, B08-SY)燒結於成膜之硬度試結果	94
表4-19 接觸角整理	97
表4-20 不同組成油墨經IPL燒結成膜之銅膜片電阻及IPL燒結參數	100
表4-21 兩種不同燒結方式之片電阻比較	101
表4-22 噴塗機操作參數	107

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