近年來，患有慢性腎臟疾病人口比例急遽增加，以往透過傳統的抽血方式來檢驗血中尿素氮含量並判斷腎臟功能是否正常，此法雖能精準得知受測者之腎臟狀況，但卻無法立即得知結果，而呼氣氨檢測在近幾年因採非侵入式且具有快速、低成本等特性，在現今社會上也已被視為具有高度潛力的檢測方式。本研究團隊致力發展有機半導體氨氣感測器，在短時間內經由簡易的呼氣方式來得到參考值，若有異常即可立即尋求醫療協助。

然而，有機材料相當懼怕大氣中的水氧，對於感測器有著一定的影響，隨著長時間使用且多次暴露在大氣環境下都會使氨氣反應與電流明顯的衰退，導致在檢測時可能因靈敏度的下降或電流訊號的不穩造成參考值的偏移，因此本論文一大主題為針對這兩大問題點進行研究，透過不同條件的測試及材料混合的方式來改善有機半導體氣體感測器之電流及氨氣反應的穩定性。

而本論文另一大主題為在量測中加入照光，探討利用光照射氨氣感測器後氨氣反應的變化及特性，並嘗試採用不同材料作為氣體感測器之主動層，並觀察其不同的特徵變化，期望藉由照光方式來提升元件之性能。

本論文分為三大部分，第一章至三章會先介紹研究動機、有機半導體氣體感測器穩定性、相關半導體製程原理及知識以及照光後材料之特性探討，第四章將會詳細探討元件氨氣反應及電流穩定性的改善，而第五章則會討論各種材料照光後之特性變化。

In recent years, the proportion of the population suffering from chronic kidney disease has increased rapidly. In the past, traditional blood sampling was used to test the blood urea nitrogen content and determine whether the kidney function is normal. Although this method can accurately know the kidney condition of the subject,but the results cannot be known immediately. In recent years, breath ammonia detection has been regarded as a detection method with high potential due to its non-invasive, rapid and low-cost characteristics.The research team is committed to developing an organic semiconductor ammonia sensor, which can obtain a reference value through a simple exhalation method in a short period of time. If there is an abnormality, you can immediately seek medical assistance.

However, organic materials are quite afraid of water and oxygen in the atmosphere, which have a certain impact on the sensor. With long-term use and multiple exposures to the atmosphere, the ammonia response and current will be significantly degraded, resulting in possible detections due to the decrease in sensitivity or the instability of the current signal and the reference value is shifted. Therefore, a major theme of this thesis is to study these two problems,improve the stability of the ammonia response and the current of the organic semiconductor gas sensor through different conditions of testing and material mixing.

Another major theme of this thesis is adding illumination to the measurement, discussing the changes and characteristics of the ammonia response after irradiating the ammonia sensor, and trying to use different materials as the active layer of the gas sensor and observe it different feature changes, it is expected that the performance of the device will be improved by lighting.

This thesis is divided into three parts. Chapters 1 to 3 will first introduce the research motivation, the stability of organic semiconductor gas sensors, the principle and knowledge of related semiconductor processes, and the discussion of the characteristics of materials after illumination. Chapter 4 will discuss in detail the stability improvement of ammonia response and the current, and the fifth chapter will discuss the characteristic changes of various materials after light irradiation.

國立清華大學電子工程究所碩士班 i
摘要 i
Abstract iii
致謝 v
目錄 viii
表目錄 xi
圖目錄 xii
第一章 序論 1
1-1 研究動機 1
1-2 氣體感測器介紹 2
1-3 先期成果 5
1-4 論文架構 7
第二章 有機材料與半導體元件介紹 8
2-1 有機材料特性與載子傳輸理論 8
2-1-1 有機材料特性 8
2-1-2 載子傳輸理論 9
2-2 有機材料氣體感測原理 12
2-3 金屬-半導體接面原理 13
2-4 有機二極體介紹 15
2-5 有機半導體氨氣感測器穩定性介紹 17
第三章 垂直式通道半導體氨氣感測器製程、量測系統 21
3-1 ITO基板電極圖案定義製程 21
3-2 垂直通道結構感測元件製程 23
3-3 量測系統介紹 28
3-4 光激發使電流回復及照光後氣體感測能力提升之特性 30
第四章 有機半導體氨氣感測器之穩定性改善 33
4-1 t-Boc系列 33
4-1-1 t-Boc(30%)元件基本特性和氣體選擇性 34
4-1-2 針對t-Boc(30%)(Annealing:190°C 1hr)進行不同保存方式之穩定性初步測試 36
4-1-3 針對t-Boc(30%)(Annealing:190°C 1hr)在大氣環境儲存條件下進行shelf lifetime測試 37
4-1-4 針對t-Boc(30%)(Annealing:80°C 2mins,150°C 15mins)在大氣環境儲存條件下進行穩定性測試 38
4-1-5 針對t-Boc(30%)(Annealing:190°C 1hr)(Annealing:80°C 2mins,150°C 15mins)兩種參數進行在氮氣包儲存條件下之穩定性測試 39
4-1-6 針對t-Boc(30%)三種參數在適當的保存方式下之穩定性探討 40
4-1-7 t-Boc(50%)不同參數之元件基本特性 43
4-1-8 針對t-Boc(50%)(Annealing:190°C 1hr) (Annealing:80°C 2mins,150°C 15mins)各兩種濃度進行在適當的保存方式下之穩定性探討 44
4-1-9 t-Boc系列之穩定性總結 46
4-2 C系列 49
4-2-1 過往C系列之穩定性介紹 49
4-2-2 針對C237調整不同參數之穩定性探討 52
4-2-3 針對C237、C246、C273(Annealing:190°C 1hr)以兩種溶劑配置下進行穩定性探討 53
4-2-4 針對C200、C250以及C200:C250=1:1,1:2,2:1(Annealing:190°C 1hr)進行穩定性探討 57
4-2-5 探討調整溶液濃度、通氣時間、流量以及濕度對於C系列的影響 59
4-2-6 C系列之穩定性總結 62
4-3 C系列混合t-Boc系列 63
4-3-1 針對C255與t-Boc(30%)(Annealing:130°C 1hr)以3種比例混合之穩定性探討 63
4-3-2 針對C237與t-Boc(30%)(Annealing:150°C 1hr)以2種比例混合之穩定性探討 64
4-3-3 針對C237與t-Boc(30%)(Annealing:190°C 1hr)以2種比例混合之穩定性探討 66
4-3-4 C系列混合t-Boc系列之穩定性總結 67
第五章 不同材料之氨氣感測器照光後特性探討 68
5-1 照光量測裝置以及相關實驗設定介紹 68
5-1-1照光量測裝置及實驗設定 68
5-1-2 利用optical power meter測出在不同電流下之LED光功率及利用thermal couple確認照光後腔體溫度變化 69
5-2 Ir(mppy)3元件照光後特性探討 70
5-2-1 Ir(mppy)3元件在玻璃外照射不同光及以不同波段LED(統一光子數相同)照射下之反應探討 70
5-2-2 Ir(mppy)3元件在玻璃內外照射不同光之反應探討 74
5-2-3 針對Ir(mppy)3進行照藍光後相關測試 75
5-3 其他有機材料照光後特性探討 78
5-3-1 PTB7元件在玻璃內外及以不同波段LED(統一光子數相同)照射下之反應探討 78
5-3-2 探討PR-02、BLUE-D、P3HT元件在玻璃內照射不同光之反應 80
5-3-3 探討CuPc、ClAlPc元件在玻璃內照射不同光之反應 82
5-3-4 探討Ir(piq)3元件在玻璃內照射不同光之反應 84
5-4 各種材料照光後特性結論 86
第六章 研究總結與未來展望 87
6-1 研究總結 87
6-2 未來展望 87
參考文獻 89

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