本研究首先利用熱脫附儀氣相層析質譜儀(TD-GC-MS)聯用系統，針對不同品種的紅酒進行氣味分析，證明透過TD-GC-MS系統可以成功分析不同品種間的差異，並找出關鍵有機氣體分子(VOCs)後，利用表面聲波(surface acoustic wave，SAW)原理發展出高靈敏度的電子鼻感測系統，使用128°YX-LiNbO3壓電材料與黃光微影製程完成感測晶片，接著搭配共振電路激發出中心頻率113~114MHz表面聲波，並懸塗高分子於感測區上並吸附關鍵有機氣體分子，藉由質量改變造成表面聲波波速變化，觀察頻率飄移下降量分析定性及定量之結果，目標發展出手持式感測裝置判定紅酒的品種以防不實的紅酒品種標榜。
本研究針對了三種品種(Cabernet sauvignon、Merlot、黑后)進行實驗，分別採購了法國藍仙姑梅洛醇釀紅葡萄酒(100% Merlot)、法國藍仙姑蘇維翁醇釀紅葡萄酒(100% Cabernet sauvignon)、藍輝酒莊國王(100% 黑后)以及涉及假酒風波的大道(Cabernet sauvignon)紅酒，透過TD-GC-MS系統證實在於黑后品種可能會散發獨特有機氣體分子: Acetic acid, methyl ester、2-Pentanone、Disulfide, dimethyl、Acetic acid, 2-methylpropyl ester以及2-Pentanol；梅洛品種可能會有獨特有機氣體分子: 2,3-Butanedione。最後利用電子鼻系統探討不同酒之頻率差異，結果發現使用PVB可以分辨出梅洛品種釀出來的酒，則PVA可以分辨黑后葡萄種類。為了提高實驗的可信度，我們進行了隨機的測試，直接利用表面聲波氣體感測器去分辨其四支紅酒透過實驗可以發現成功分辨出四支紅酒。

In this research, thermal desorption tendon with gas chromatography-mass spectrum (GC-MS) system has been used to find the marker of VOCs in red wine with different grape varieties. After getting the marker, we utilize the principle of surface acoustic wave (SAW) to develop a highly sensitive electronic nose sensing system for detecting the marker. 113~114MHz SAW chips are fabricated by MEMS techniques with lithography process; gold interdigital transducers and heater line are deposited on the 128°YX-LiNbO3. The adsorption of VOCs by coating polymer on sensing area will modulate the velocity of acoustic wave because of the loading effect. Therefore, we can observe the frequency shift to identify the VOCs and the limited concentration. Our goal is to develop a portable sensing device for analyzing the aroma of red wine to discriminate the different grape varieties.
This report experiments with three grape varieties(Cabernet sauvignon、Merlot、blackqueen), which is Blue Nun Merlot(100% Merlot)、Blue Nun Cabernet sauvignon (100% Cabernet sauvignon)、King(100% blackqueen)from LH winery in Taiwan, and the probably fake red wine(Dadung with Cabernet sauvignon). As a result, the blackqueen grape variety possibly has unique VOCs, which are Acetic acid, methyl ester、2-Pentanone、Disulfide, dimethyl、Acetic acid, 2-methylpropyl ester and 2-Pentanol; Merlot grape variety probably has special VOCs such that 2,3-Butanedione. Then, we can use SAW system to detect the aroma of red wine and determine the frequency shift to distinguish between them. The results show that using PVB as detecting material can distinguish Merlot from the others where as PVA can differentiate blackqueen from the others. Finally, we conducted the random test to prove the accuracy of SAW sensors. As a result, our SAW sensor can successfully distinguish between them.

摘要..................i
Abstract.............ii
致謝.................iii
圖目錄...............viii
表目錄.................xi
1.緒論..................0
1.1研究動機.............0
1.2研究目標.............1
1.2.1熱脫附氣相層析質譜儀對於紅酒氣味分析目標...... 1
1.2.2表面聲波感測器對於紅酒氣味分析目標........... 2
2.文獻回顧...................................... 3
2.1 氣體分析方法................................ 3
2.1.1 FTIR..................................... 3
2.1.2 FID...................................... 4
2.1.3 GC-MS.................................... 5
2.2 樣品預濃縮.................................. 6
2.2.1 固相微萃取(SPME).......................... 6
2.2.2 熱脫附(TD)................................ 6
2.3氣體感測器介紹............................... 7
2.3.1氣體感測器應用介紹.......................... 8
2.3.2氣體感測器種類............................. 8
2.3.3.1半導體氣體感測器(Metal oxide semiconductor gas sensor)... 8
2.3.3.2紅外線氣體感測器(Infrared gas sensor).................... 9
2.3.3.3石英晶體微量天秤(Quartz crystal microbalance)............ 10
2.3.3.4光離子化偵測器(Photo ionization detector)................ 10
2.3.3.5表面聲波氣體感測器(Surface acoustic wave gas sensor)..... 11
2.3.3.6各種電子鼻之比較......................................... 11
2.4紅酒氣體分析及感測之相關文獻.................................. 13
3.表面聲波感測器介紹及其原理..................................... 16
3.1表面聲波.................................................... 16
3.2壓電材料.................................................... 17
3.2.1壓電基板的材料種類及參數................................... 18
3.2.2壓電基材的插入損失( insertion loss，IL )................... 20
3.3指叉式電極轉換器( interdigital transducers，IDT )............ 22
3.4壓電效應.................................................... 25
3.5表面聲波感測機制............................................. 28
4.表面聲波感測器設計............................................ 30
4.1表面聲波晶片設計及製程........................................ 30
4.1.1表面聲波晶片設計........................................... 30
4.1.2黃光製程.................................................. 32
4.2震盪電路設計................................................. 36
4.3塗佈感測薄膜................................................. 38
4.3.1高分子塗佈方式............................................. 39
4.3.2高分子吸附形式............................................. 39
4.3.3高分子選擇................................................. 41
5.實驗參數設計及量測系統架設..................................... 43
5.1 TD-GC-MS................................................... 43
5.1.1 採樣管介紹與校正(Conditioning)............................ 43
5.1.2 樣品採樣................................................. 44
5.1.3 實驗參數設計............................................. 45
5.1.3.1 熱脫附儀(TD)........................................... 45
5.1.3.2 氣相層析質譜儀(GC-MS)................................... 46
5.1.4 數據分析................................................. 47
5.1.4.1 滯留時間(Retention time, RT)........................... 47
5.1.4.2 訊號峰高度(Peak height)................................ 47
5.1.4.3 訊號峰面積(Peak Area).................................. 48
5.2 表面聲波陣列氣體感測器( SAW sensor array)................... 49
5.2.1 實驗所需之儀器........................................... 49
5.2.2 微腔體設計............................................... 54
5.2.3 實驗步驟................................................. 55
6.實驗結果與討論............................................... 58
6.1 熱脫附氣相層析質譜儀結果..................................... 58
6.1.1 層析管柱DB-624分析結果.................................... 59
6.1.2 層析管柱DB-WAX分析結果.................................... 62
6.1.3 再現性................................................... 63
6.2 表面聲波陣列氣體感測器結果................................... 66
6.2.1 2-ports表面穩定性測試..................................... 66
6.2.2 4-ports系統穩定性測試..................................... 68
6.2.3 紅酒氣味量測............................................. 71
6.2.3.1 感測材料: PVB.......................................... 72
6.2.3.2 感測材料: PVA.......................................... 75
6.2.3.3 感測材料: P4VP......................................... 77
6.2.3.4 感測材料: PS........................................... 79
6.2.3.5 感測材料: PNVP......................................... 82
6.2.3.6 感測材料: PMMA......................................... 84
6.2.3.7 六種高分子以及Figaro sensor對於紅酒反應比較.............. 86
6.3 紅酒隨機量測............................................... 90
7.結論與未來進度............................................... 93
8.參考文獻..................................................... 96

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