蠶絲蛋白 (silk fibroin) 由蠶繭脫膠後萃取而得，靛藍 (indigo, C16H10N2O2)是常用於衣物染色之天然染料，已有文獻描述具雙載子特性。本實驗以水溶液製程蠶絲蛋白為介電層、熱蒸鍍靛藍薄膜為半導體，製備生物相容有機薄膜電晶體，並評估於不同環境濕度下元件電性表現。靛藍薄膜結晶性可藉由TTC
(Tetratetracontane, C44H90) 層間層加入而改善，並使元件表現雙載子特性。真空下，元件p 型及n 型飽和區載子遷移率分別為9 × 10−5與0.05cm2V−1s−1，臨介電壓 (Vth) 分別為-90V 與80V；有高的n 型載子遷移率，但與p 型載子遷移率差異大，且操作偏壓高。於相對濕度20% ~ 50%下量測元件電性，發現在濕度30%下，元件有相近的n 型與p 型載子遷移率約為10−2cm2V−1s−1，臨
介電壓約為±60V，是合適的元件操作濕度。若於濕度50%下量測元件，雖臨介電壓降至約為±30V，但n 型載子遷移率下降至10−3cm2V−1s−1。蠶絲蛋白組成胺基酸包括：絲胺酸 (Serine)、丙胺酸 (Alanine)、甘胺酸 (Glycine)；其中，絲胺酸為極性胺基酸、氮氧原子上孤對電子、蛋白質碳端與氮端皆可能是使蠶絲蛋白具吸水性原因。含水環境下蠶絲蛋白介電層累積載子能力增加，而靛藍半導體則降低傳輸，推測所觀察之電性隨濕度變化為兩因素之抗衡。遲滯曲線量測結果為反向掃描汲極電流大於正向掃描電流，含水環境下遲滯曲線較真空下減少許多。

Silk fibroin is a natural protein extracted from Cocoons of Bombyx mori.
Indigo (C16H10N2O2) is a natural dye pigment used extensively on commodities and
has been reported to have ambipolar transport characteristics. The objective of this
work is to fabricate Bio-organic thin film transistors (Bio-OTFTs) by integrating
thermal evaporated indigo thin film and solution-based silk fibroin and to evaluate
the performance of ambipolar devices at different relative humidity. The crystal
quality of indigo is improved by inserting a TTC (Tetratetracontane, C44H90)
interlayer on silk fibroin so that both the p- and n- channel transport appear
simultaneously in the indigo ambipolar Bio-OTFT. In vacuum, the operation voltage
is up to 100 V and the p- and n- channel field effect mobility (μFE,sat) are
respectively ca. 9 × 10−5 and 0.05cm2V−1s−1 in saturation region and the
threshold voltages (VTH) are ca. -90 V and 80 V, respectively. In air ambient, the
amino acid including Glycine, Serine and Alanine in silk fibroin make silk fibroin a
hygroscopic dielectric material. At 30% relative humidity, the indigo ambipolar
OTFT exhibits comparable μFE,sat of ca. 10−2cm2V−1s−1 for hole and electron.
While the relative humidity increases to ca. 50%, the VTH reduces to ca. ±30 V but
with a worse n-channel performance ca. 10−3cm2V−1s−1. Hysteresis shows a higher
back scanning current and a larger VTH shift in vacuum than in 55% relative humidity
during gate voltage sweep.

摘要 I
Abstract II
誌謝 III
圖目錄 IV
表目錄 VII
第一章 緒論 1
1-1前言 1
1-2研究動機 2
1-3有機薄膜電晶體結構與操作原理 3
1-4 OTFT效能擷取 5
1-4-1載子遷移率 5
1-4-2臨界電壓 5
1-4-3開關電流比 6
1-5有機半導體 (OSC) 載子傳輸機制 6
1-6雙載子有機薄膜電晶體 8
1-6-1 雙載子有機薄膜電晶體基本操作 8
第二章 文獻回顧 10
2-1 生物有機電子 10
2-1-1介電層與層間層 (interlayer) 發展 10
2-1-2有機半導體發展 11
2-2靛藍 (indigo) 染料簡介 13
2-2-1 indigo染料發展 13
2-2-2 indigo薄膜應用於電子元件 14
2-2-3 indigo應用於有機薄膜電晶體 15
2-2-4 indigo的氫鍵 (H-bonding) 15
2-3吸水性蛋白質介電材料 16
2-4遲滯現象成因 17
2-5 Tetratetracontane (C44H90, TTC) 層間層 18
2-6 元件n型載子空氣穩定性 19
第三章 研究流程與方法 20
3-1 蠶絲蛋白製備及旋轉塗佈 22
3-1-1 蠶絲蛋白溶液製備 22
3-1-2旋轉塗佈 (spin coating) 製程 23
3-2有機小分子及金屬熱蒸鍍 23
3-2-1熱蒸鍍原理及真空配置 23
3-2-2 熱蒸鍍使用之藥品名細 24
3-3基板製備 24
3-4 量測環境濕度控制 24
3-5 分析儀器 25
3-5-1 原子力顯微鏡 ( AFM) 25
3-5-2低掠角X光繞射分析 (GIXRD) 26
3-5-3 掃描式電子顯微鏡 (SEM) 27
3-5-4有機薄膜電晶體電性量測 28
3-5-5準靜態電容電壓量測 (QSCV) 28
第四章 結果與討論 30
4-1 indigo薄膜與蠶絲蛋白介電層搭配 30
4-2 加入C44H90 (TTC) 層間層 (interlayer) 能改善電性 31
4-3 TTC層間層對indigo薄膜影響及形貌最佳化 32
4-3-1 使用TTC層間層對indigo薄膜表面形貌影響 32
4-3-2 使用TTC層間層對indigo薄膜結晶性影響 33
4-3-3 TTC層間層之表面形貌及熱處理 34
4-3-4 元件電性量測 35
4-3-5真空下電性量測以排除環境濕度影響 36
4-4 濕度對吸水性蠶絲蛋白為介電層之indigo雙載子有機薄膜電晶體影響 39
4-4-1 indigo ambipolar OTFT 於不同相對溼度下電性表現 40
4-4-2 遲滯現象 48
第五章 結論 50
第六章 未來展望 51
參考文獻 52
附錄一 56
附錄二 58

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