雷射直寫自還原金屬複合墨水製作高抗氧化銅鎳合金網格透明電極

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張喬博(CHIAO-PO CHANG) 查詢紙本館藏

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機械工程學系

論文名稱

雷射直寫自還原金屬複合墨水製作高抗氧化銅鎳合金網格透明電極
(Fabrication of Oxidation Resistant, Cu-Ni Alloy Metal-mesh Transparent Electrode by Laser Direct Write from Self-Reduction Metal Complex Inks)

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摘要(中)

銦錫氧化物(Indium tin oxide, ITO)具有著良好的透光度以及導電性，在透明電極發展中有著相當重要的地位，然而ITO相當缺乏機械性質，無法應用於發展中的撓性面板或穿戴式電子產品的電極。大量的研究指出透過金屬金、銀、銅製作的可撓電極有很大的機會可以取代ITO，然而金、銀昂貴，銅容易因為氧化失去電性，故本研究旨在開發一種可以降低成本且壽命較長的銅鎳合金電極，並以可在大氣環境下直接製作之雷射直寫技術製造，最後在高溫環境檢測不同銅鎳成份比合金電極之電性變化。
甲酸鎳和甲酸銅皆為可加熱自還原的有機金屬鹽類，最大的優點是無須還原劑。本研究透過混合不同莫耳數比的甲酸銅以及甲酸鎳於有機溶劑中，將製備完成的複合金屬墨水塗佈於玻璃基板形成均勻薄膜，透過50倍聚焦532 nm綠光雷射誘發甲酸銅以及甲酸鎳的熱分解並且燒結，搭配移動平台可以在無需光罩且在大氣環境下進行金屬的圖案化，透過上述方法可以製作出片電阻 70 Ω/□、透光度大於80%、平均厚度500 nm的透明銅鎳合金網格電極。
研究指出銅在高溫環境下會因為氧化而大幅度提升電阻，於本研究中，將純銅網格電極以及不同比例的銅鎳網格電極放置於250 °C加熱器上，銅網格電極在1~2小時電阻值變化約為106 倍，而銅鎳網格電極(溶液中Cu:Ni=1:2)經過48小時電阻值變化不超過3倍。

摘要(英)

Indium tin oxide, ITO, has good performance in both transmittance and conductivity. Thus, it has been playing an important role in transparent conducting electrodes. However, ITO is brittle that restricts its applications in the blooming flexible electrotrincs. Many research reports reveal that metal-mesh-based electrodes by varios metal materials such as gold, silver, and copper, have demonstrated high potential as alternative transparent electrodes. However, gold and silver are too expensive and copper is easy to get oxidated either at the duration of fabricating process or in the course of operations. Thus, this study is committing to develop a low-cost alloy electrode that is with high oxidation resistance. We aim to develop a copper-nickel-alloy-based metal mesh electrode fabricated by the technique of laser direct write. The resulting capability in oxidation resistance is tested in an elevated temperature environment.
Copper formate and nickel formate are all metal organic thermal decomposition (MOD) compounds that take the advantages in both reducing to metal ions without the need of any reducing agents and obtaining the resulting various compound solutions by mixing both inks at different molar ratios. The mixed MOD solution is then spin-coated on a glass substrate and dried in vacuum at 100 °C to form a uniform MOD thin film. It is then heated by a focused 532 nm laser beam to induce thermal decompositons of both copper formate and nickel formate and sintered reduced copper and nickel particles. The pattern of the resulting metal-mesh can be accomplished by laser direct wirte, a maskless process and executable in the ambient. Results show that the fabricated copper-nickel alloy electrode exhibit good characterisitics: sheet resistance less than 70 Ω/□, transmittance over 80% and the average thickness about 500 nm.
Copper is very easy to get oxided, expecially at high temperatures. The excellent ability in oxidation resistance of our copper-nickel mesh elelctrode is examined in an oven maintaining at temperature up to 250 °C for 48 hours. The resistance increasement is only 3 folds, which is much more smaller than that of a copper mesh electrode that shows 106 times in resistance enhancement.

關鍵字(中)

★ 雷射直寫
★ 透明電極
★ 自還原
★ 合金網格電極

關鍵字(英)

論文目次

摘要 iii
Abstract iv
目錄 v
圖目錄 viii
表目錄 xi
Chapter 1 緒論 1
1-1 前言 1
1-2 研究背景、目的與方法 3
Chapter 2 文獻回顧與基礎理論 5
2-1 金屬電極 5
2-1-1 物理汽相沉積圖案化金屬製程 5
2-1-2 氙燈製程燒結金屬薄膜 7
2-1-3 噴墨製程 9
2-1-4 化學鍍製作透明電極 12
2-1-5 金屬奈米線 13
2-2 熱還原金屬墨水 16
2-3 雷射直寫技術 20
2-4 銅抗氧化 25
2-5 傳承與創新 28
Chapter 3 實驗方法 29
3-1 實驗流程與方法 29
3-2 實驗步驟 30
3-2-1 玻璃基板處理 30
3-2-2 甲酸銅以及甲酸鎳配製具自還原性有機金屬墨水 30
3-2-3 薄膜製備 30
3-2-4 雷射誘發有機金屬熱分解 30
3-3 實驗用品 31
3-4 材料檢測分析儀器 33
3-4-1 單晶X光繞射儀 (Single-Crystal X-ray Diffraction, XRD) 33
3-4-2 熱重分析儀 (Thermogravimetric analysis, TGA) 33
3-4-3 場發掃描式電子顯微鏡 (Field-emmision Scanning Electronic Microscopy, FE-SEM) 34
3-4-4 高解析掃描穿透式電子顯微鏡 34
Chapter 4 結果與討論 35
4-1 材料製備結果 35
4-1-1 甲酸銅/甲酸鎳/1-氨基-2丙醇/異丙醇金屬墨水 35
4-2 雷射直寫 38
4-2-1 雷射誘發熱分解以及燒結銅鎳形成合金導線 38
4-3 表面形貌與成份分析 38
4-3-1 溶液內銅：鎳=1：1之表面形貌以及成份分析 38
4-3-2 溶液內銅：鎳=2：1之表面形貌以及成份分析 42
4-3-3 溶液內銅：鎳=1：2之表面形貌以及成份分析 46
4-3-4 以300°C加熱Cu:Ni=1:2 50
4-3-5 添加更多1-胺基-2-丙醇，Cu:Ni=1:2 53
4-3-6 添加更多1-胺基-2-丙醇，Cu:Ni=1:4，並且以兩台EDS檢測 54
4-3-7 小結 56
4-4 金屬固溶探討 57
4-4-1 Hume-Rothery rules 58
4-4-2 Bragg’s law 58
4-4-3 XRD、HRTEM分析 59
4-5 電極特性 63
Chapter 5 結論與未來工作 68
5-1 結論 68
5-2 未來工作 68
參考文獻 70
碩士論文口試教授問題集 74

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指導教授

何正榮

審核日期

2018-8-23

推文