本研究提出一種新穎製程用以製造奈米銀導電乙醇墨水的奈米銀棒，我們使用晶種合成法以UV曝光後的奈米氯化銀顆粒作為晶種，在120℃環境下加入聚乙烯吡咯烷酮(PVP)及硝酸銀合成高展弦比約1055的奈米銀線溶液，在室溫下利用磁石攪拌通過孔隙率94.8%平均孔洞大小約2mm的多孔性發泡鋁，經4天後得到展弦比約130的奈米銀棒，利用奈米銀棒調配25wt%臨界濃度的奈米銀導電乙醇墨水，以鋼筆在紙張上繪製成寬度為1毫米的導電線段，其片電阻約為0.018Ω/sq。

The present study has been purposed a novel process for manufacturing conductive ink consists of silver nanorods with ethanol and coated it on the paper to a conductive line with low sheet resistance. First, we synthesized the silver nanowires solution using the irradiated nano silver chloride particles by UV irradiation as a seed crystal and seed synthesis method. Then the silver nanowires solution was magnetic agitated and passed through a foamed aluminum with porosity about 95% and average pore size about 2mm at 25°C for 96 hours. The average aspect ratio of silver nanowires will be decreased from 1055 to 130 via. silver nanowires were chopped by erosion with foamed aluminum and we fabricated successful a conductive ink which consist of 26wt% of ethanol mixed with nano silver rods and then coated a conductive line with width of 1mm on the matte paper by pen which the sheet resistance of conductive line reached 0.018 Ω/sq.

第1章 導論                                               1 
1 1前言                                                 1 
1 2文獻回顧                                              4 
1 2 1奈米銀線性質                                        4 
1 2 2奈米銀線的製備方法                                   4 
1 2 2 1模板合成法                                        4 
1 2 2 2晶種合成法                                        7 
1 2 2 3 多元醇合成法                                    11 
1 2 3俱旗幟型奈米銀線                                    14 
1 2 4 滲透理論                                          16 
1 2 5奈米銀導電墨水                                     18 
1 3研究動機                                             25 
第2章 實驗設計                                          26 
2 1實驗材料與設備                                       26 
2 1 1實驗材料                                           26 
2 1 2實驗設備                                           27 
2 2實驗步驟                                             28 
2 2 1氯化銀晶種的製備                                    28 
2 2 2奈米銀線的製作                                     29 
2 2 3奈米銀線的純化                                     29 
2 2 4奈米銀線的PVP去除及重新成長                          30 
2 3顯微結構觀察                                         31 
2 3 1 穿透式電子顯微鏡(TEM)                              31 
2 3 2共軛焦顯微鏡                                       31 
2 3 3四點探針測試儀                                     32 
第3章 結果與討論                                        33 
3 1晶種合成法之奈米銀線                                  33 
3 2不同轉速對奈米銀線展弦比的影響                         36 
3 3低展弦比奈米銀線的導電測試                             53 
3 4低展弦比奈米銀線印刷                                  60 
圖目錄 
圖1-1 (a)AAO模板AFM圖;(b)AAO模板截面的FE-SEM圖[11]        5 
圖1-2 AAO模板移除後的奈米銀線陣列SEM圖（a）上視圖;（b）上視放大圖;（c）橫截面;（d）較短的奈米銀線圖[11]                 6 
圖1-3 銀的製備SEM圖 (a)加熱速率40℃/h 、0 1mol/L硝酸銀溶液; (b)加熱速率40℃/h 、0 5mol/L硝酸銀溶液;(c) 加熱速率40℃/h 、1 0mol/L硝酸銀溶液;(d) 加熱速率240℃/h 、0 1mol/L硝酸銀溶液[12]                                                    7 
圖1-4 晶種合成法步驟示意圖:利用銀晶種合成奈米銀線[13]        8 
圖1-5 ITO先浸漬在種子溶液2小時後，浸漬在含有0 12ml抗壞血酸的生長溶液24小時後(a)倍率較大;(b)倍率較小 含有奈米銀顆粒的FE-SEM照片[16]                                                 10 
圖1-6 通過加入不同濃度的硝酸銀生長出不同展弦比的銀[19]      12 
圖1-7 雙五面體銀晶種成長為奈米銀線[19]                    12 
圖1-8 多元醇合成法製備奈米銀線，加入銅鹽之反應[20]          13 
圖1-9 多元醇法利用鉑晶種製備奈米銀線步驟示意圖[21]          14 
圖1-10 (a)奈米銀棒 (b~f) 在不同之DMF溶液中不同的[AgNO3]1/[AgNO3]2比值生長的旗幟型態奈米銀結構[22]         16 
圖1-11 (a)乾燥後均勻的銀產物;(b)銀晶體的尺寸大小之SEM照片[24]                                                        19 
圖1-12 相對時間給予墨水的溫度分佈導致的質量損失百分比[24]   20 

圖1-13 製備樣品的圖案與尺寸[25]                          22 
圖1-14 導電墨水A、B在不同基材上的片電阻[25]               22 
圖1-15 三種加熱的方法用不同時間乾燥後的片電阻測量[26]       24 
圖2-1 奈米銀線利用磁石攪拌機流經發泡鋁多孔性結構的示意圖     30 
圖3-1 繞射分析儀(X-ray diffractometer，XRD)分析奈米氯化銀顆粒表面銀原子簇的晶相                                     34 
圖3-2 在120℃環境下合成具有高展弦比奈米銀線的(a)共軛焦顯微照片;(b)TEM顯微照片                                          35 
圖3-3 奈米銀線溶液以不同轉速通過多孔性發泡鋁後再生長之共軛顯照片;轉速為(a)0 rpm;(b)200 rpm ;(c)400 rpm; (d)600 rpm; (e)800 rpm; (f)1000rpm                                 37 
圖3-4 奈米銀線以不同轉速通過多孔性發泡鋁的共軛顯微照片(a)0 rpm;(b)200 rpm ;(c)400 rpm; (d)600 rpm; (e)800 rpm; (f)1000 rpm                                            38 
圖3-5 奈米銀線PVP刮除及再成長示意圖                       39 
圖3-6 流場A為水平快速與發泡鋁碰撞或穿過，流場B為上下對流的示意圖                                                     40 
圖3-7 奈米銀線以400rpm經過多孔性發泡鋁同時出現折彎及折斷的共軛顯微照片                                                41 
圖3-8 奈米銀線溶液以400 rpm磁石攪拌通過多孔性發泡鋁，時間為 (a)0 小時(b)1 小時;(c)2小時; (d)3小時;(e) 4小時;(f)5小時;(g)6小時;(h)7小時;(i)8小時; (j)9時;(k)10小時;(l) 11小時;(m)12小時的共軛焦照片                                    49 
圖3-9 奈米銀線溶液以400 rpm磁石攪拌通過多孔性發泡鋁，時間為(a)0小時;(b)12小時; (c)1天;(d) 2天;(e)3天;(f)4天的共軛焦照片                                                        52 
圖3-10 奈米銀線在0小時、12小時、1天、2天、3天、4天平均展弦比與攪拌時間的關係圖                                         54 
圖3-11 奈米銀線溶液；奈米銀棒含量(a)5wt%;(b)10wt%;(c)15wt%;(d)20wt%;(e)25wt%;(f)30wt%;(g)35wt%;(h)40wt%，厚度3微米的塗層的共軛焦顯微結構                                     59 
圖3-12 (a)一般A4紙張;(b)西卡紙紙張;(c)雪銅紙纖維的共軛焦顯微照片                                                     62 
圖3-13 在雪銅紙上以26wt%奈米銀棒溶液利用鋼筆繪製線段的共軛焦顯微照片                                                 63 
圖3-14 以26wt%奈米銀棒溶液利用鋼筆繪製的簡易電路圖         63 
表目錄 
表1-1 不同濃度奈米銀線的片電阻及可見光穿透率[7]             2 
表1-2 三種導電墨水性質[25]                               21 
表3-1 低展弦比奈米銀棒溶液25~40wt%，於玻璃基板塗佈3微米塗層的片電阻值(Ω/sq)                                          55

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