柔軟且可伸展的導電結構是穿戴式感測器不可或缺的關鍵元素，通常是透過
在彈性聚合物基材上嵌入導電材料而成。本研究開發快速的複合導電結構成型技術，使用彈性高分子聚二甲基矽氧烷做為應變感測器的基材，並在表面沉積具備良好機械特性的導電高分子聚吡咯，以及優異導電特性的銀奈米顆粒，組成兼具機械感測與電流傳導功能的複合結構。本研究使用光致聚合的方式在彈性基材上定義出聚吡咯導線的圖形，為提高導電度，進一步嵌入密緻的銀奈米顆粒，並覆蓋化學聚合產生的聚吡咯。整個複合結構的製作可分四步驟在8分鐘之內完成，圖形定義精度可達0.01英吋，電導率可達34.95 S/cm，1 cm長1 mm寬的導線電阻約為800 Ω。
本研究所製作的複合導電結構其電阻隨應變增加而上升，具有電阻式應變感測的功能。為提升其伸展性，還透過預先拉伸基材的方式，將表面拉伸至200%應變的狀態再沉積導電結構，之後卸除外力使其回復原狀。因為複合結構與彈性基材的尺寸和機械特性差異極大，會使回復後的導線產生微觀的波浪狀皺摺結構。這些皺摺結構可有效提升導線的伸展性，在200%應變範圍內電阻幾乎保持定值。為了展示本研究複合導電結構的實用價值，我們使用DLP光固化三維列印系統，列印能依照指圍大小調整的手指穿戴結構，並整合前述的彈性基材與複合導線，形成一可感測手指姿態的電阻式應變感測器。此一技術未來可望應用於人體關節，以及軟性機械運動的感測，產生回饋訊號以完備系統的控制與整合。

Soft and stretchable conductive materials are highly desired for the implementation of wearable electronic devices. Electronics can be made on elastically stretchable substrates, which conform to irregularly curved surfaces of human skin. For example, skin-mountable and wearable sensors are needed for applications including body motion detection, personalized health-monitoring, and the feedback control of soft robotics. Conducting polymers, whose chemical and physical properties can be tailored to the specific needs of many applications, are commonly used in stretchable electronics. However, the manufacturing of stretchable conducting polymer structures is usually costly and time-consuming, and the stretchability of resulting structures is normally limited. The goal of this thesis is to develop a rapid prototyping scheme of soft conductive composites for wearable sensors. We have developed various patterning processes that simultaneously deposit electronically conducting poly-pyrrole structures and incorporate nanophase silver grains within. Meanwhile, the spatial distribution of silver grains can be locally adjusted to improve the conductivity of composite structures.
A four-step rapid manufacturing scheme based on (1) photo-polymerization of silver-containing polypyrrole films, (2) photo-deposition of additional silver particles on surface, (3) further growth of silver particles on surface, and (4) lift-off deposition of silver-containing polypyrrole films, has been implemented successfully. Pyrrole molecules can be oxidized with either cationic photo-initiators or silver ions, and polymerized into desired polypyrrole patterns on elastomeric polydimethylsiloxane (PDMS) substrates. If the elastic PDMS substrates are pre-stretched, it results in the wrinkling of relative rigid silver-containing polypyrrole films on surface. The buckled, wavy polypyrrole films are promising candidates for interconnects in stretchable electronics. It is demonstrated that the polypyrrole films remains electrically conductive up to >250% strain and maintains electrical continuity under repeated mechanical deformation. Overall, the proto-typing of conductive composites with line width down to 0.01 inches can be completed in 8 minutes. The conductivity of resulting silver-containing polypyrrole structures is measured to be higher than 35 S/cm. In the prototype demonstration, DLP (digital light processing) stereolithography is employed to selectively deposit conductive composite structures on demand, and to build wearable monitors to measure finger postures.

摘要 i
目錄 v
圖目錄 x
表目錄 xv
第一章、緒論 1
1.1 前言 1
1.2 導電高分子 (Conductive polymer) 2
1.2.1 導電高分子導電機理 2
1.2.2 導電高分子應用 3
1.3 奈米金屬顆粒 4
1.4 三維列印 5
1.4.1 三維列印技術介紹 5
1.4.2 光固化三維列印 6
1.5 光聚合反應 (Photo-polymerization) 7
1.5.1 自由基型聚合反應 7
1.5.2 陽離子型聚合反應 8
1.6 可穿戴式感測器 9
1.6.1 電容式與電阻式應變感測器 10
1.7 多波長光固化彈性體 11
1.8 研究動機與目的 12
第二章、文獻回顧 13
2.1導電高分子 13
2.1.1導電高分子介紹 13
2.1.2 導電高分子的合成 15
2.1.3 光聚合含銀的導電高分子薄膜 18
2.1.4 奈米金屬銀/樹酯複合材料 22
2.1.5 導電高分子感測器 24
2.2 奈米銀粒子 26
2.2.1 光還原銀奈米顆粒 27
2.2.2 銀奈米顆粒的成核與成長 27
2.2.3 顯影劑介紹 28
2.3 高分子彈性體 30
2.3.1 光固化彈性高分子 30
2.3.2 PDMS / Dragon Skin 複合材料 30
2.4 應變感測器設計 31
2.5.1拉伸應變感測器 31
2.5.2 DLP系統整合之感測器 32
第三章、實驗原理與設計 34
3.1 實驗機台介紹 34
3.1.1 DLP機台介紹 34
3.1.2 DLP製造流程 35
3.1.3 拉伸測試機台介紹 37
3.1.4 其他實驗設備與儀器 38
3.2 實驗室材料介紹 38
3.2.1聚吡咯/銀複合導線溶液成分 38
3.2.2 感光性保護層成分 42
3.2.3 化學聚合聚吡咯溶液成分 44
3.3 聚吡咯/銀複合導線製程 45
3.3.1四步光誘導聚吡咯/銀複合導線製程原理 45
3.3.2 第一步底層聚吡咯聚合過程 46
3.3.3 銀核增密 48
3.3.4 銀粒子成長 49
3.3.5 二次聚合 50
3.3.6 聚吡咯/銀粒子複合導線製程 50
3.4 感測器彈性基材 54
3.4.1 PDMS / Ecoflex 複合材料可拉伸性 54
3.4.2 PDMS厚度與轉速的關係 55
3.4.3 預先拉伸PDMS / Ecoflex 複合材料 55
3.5 剝離成形製程(Lift-off patterning) 57
3.5.1 剝離成形製程原理 57
3.5.2 感光性保護層 58
3.5.3 聚吡咯化學聚合 58
3.6應變感測器設計與製作 60
第四章、研究結果與分析 62
4.1 銀/聚吡咯複合導線 62
4.1.1 光聚合配方濃度與銀粒子生長關係 63
4.1.2 照射時間對複合導線中銀膜生成的關係 65
4.1.3 溫度對複合導線中銀膜電阻的關係 66
4.2 剝離成形導線(Lift-off partterning) 68
4.2.2 吡咯濃度與電阻關係 70
4.2.3 摻雜劑濃度與電阻關係 70
4.2.4氧化劑濃度與電阻關係 71
4.2.5 感光性保護層 72
4.3複合導線彎曲測試 75
4.4複合導線拉伸測試 77
4.4.1銀核增密對於可拉伸性之影響 77
4.4.2 二次聚合對於可拉伸性之影響 78
4.4.3 複合導線靈敏度與線性度 79
4.4.5複合導線耐久度測試 81
4.4.6 基材預拉伸之複合導線拉伸測試 82
4.5 複合導線方向性測試 86
4.6 穿戴式應變感測器 88
4.6.1 穿戴式應變感測器實體 88
4.6.2 應變感測器彎曲測試 88
第五章、 結論 91
5.1 光定位聚吡咯/銀粒子複合導線 91
5.2 剝離成形製程 91
5.3 整合感測器 92
第六章、 未來建議 93
6.1複合導線改良 93
6.2 感測器應用開發 93
參考資料 95

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