在本研究中，我們製備出低成本、環境友善且具有高靈敏度的紙基感測器，並將其應用在食品安全以及重金屬檢測。在第一部分的研究中，我們首先製備出具有單層金屬奈米粒子之模板，接著利用奈米壓印製程將金屬奈米粒子轉印至紙基材上。其中，我們分析了11種生活中常見的紙基材，並選取具有高反射率及在壓印過程中呈現高穩定性的噴墨相片紙作為本研究中製備紙基感測器之紙基材。接著，我們探討將金屬奈米粒子轉印至噴墨相片紙的製程參數：為了最佳化紙基感測器的靈敏度，我們藉由調控壓力及溫度參數，成功將金屬奈米粒子大面積且均勻的轉印至紙基上，並使得金屬奈米粒子仍保有可與待測分子作用的表面積，接著結合光學影像的巨觀分析，以及利用SEM及AFM來觀察微觀的壓印結果。最後，我們選擇加熱溫度80 °C以及加壓壓力40 Kg/cm2為製備紙基感測器的最佳化製程參數。紙基感測器製備完成後，我們將其應用在檢測海鮮食品於腐敗過程中所釋放的生物胺，並藉著紙基感測器之顏色變化來判斷其新鮮度。其中，我們選擇腐胺（Putrescine）作為本研究中的待測物分子，由於揮發性的腐胺分子附著在金屬奈米粒子表面時，會造成金屬奈米粒子周圍環境折射率上升，而導致紙基感測器的反射光譜圖其吸收波谷位置會隨之紅移，當腐胺濃度提高時，紙基感測器的波谷位置之波長呈現線性變化。接著，我們將本研究之紙基感測器應用於檢測實際含有腐胺分子的鮭魚樣品，並呈現了預期的波長變化，代表本研究的紙基感測器確實可應用在檢測海鮮食品新鮮度。在這部分的實驗，我們成功製備出具有單層金屬奈米粒子的結構，並且具備了可撓性、拋棄式、環境友善以及低成本的紙基感測器，也將之應用在食品檢測上。
在第二部分的研究中，我們利用前述開發的紙基感測器來檢測環境中的重金屬汙染—汞。當奈米銀粒子與汞離子接觸後會發生自發性氧化還原反應，同時產生汞合金（汞齊）；而銀含量的逐漸損耗則會伴隨著表面電漿共振的特性迅速衰減，同時產生明顯的顏色變化，所以本研究藉由肉眼判斷顏色變化而得知檢測樣品內汞離子的濃度高低。首先，我們在奈米粒子水溶液內檢測汞離子，並且比較了三種奈米粒子對汞離子的靈敏度，分別為：（1）銀奈米粒子（2）中空金奈米粒子（3）銀殼層包覆之中空金奈米粒子。我們發現，銀奈米粒子的靈敏度最高，並且以銀奈米粒子以及中空金奈米粒子做了兩組溶液相的檢量線。接下來，我們利用銀奈米粒子搭配奈米壓印以及自組裝的方式來製備紙基感測器以及PET （聚對苯二甲酸乙二酯）感測器，並分析與汞離子反應前後之光譜變化與顏色變化。由於紙張的吸水特性會干擾到光譜訊號的判讀，因此我們選擇PET感測器做為後續製程的最佳化模板；製程最佳化的部分包含了空白試驗的最佳化、銀奈米粒子的選擇以及奈米粒子的密度。最後，我們以最佳化之PET感測器對環境污染中常見之金屬離子做選擇性測試，證實本研究確實對汞離子有較高靈敏度。
綜合以上，本研究研發出低成本、可燃、輕量及易使用之紙基感測器，不只可應用在食品新鮮度之監控，也可應用在環境汙染之檢測。

In this thesis, we successfully fabricated a low-cost, eco-friendly and highly sensitive paper-based plasmonic sensor for the detection of food safety and heavy metal ions. In the first part of this thesis, we first prepared molds with monolayer of metal nanoparticles (NPs) via self-assembly. Then, we transferred the metal NPs from the mold onto the paper by nanoimprinting process. 11 types of daily-used papers were examined according to their optical, mechanical and thermal properties, then we found the inkjet paper is an excellent substrate with highly-reflective surface and great stability under the imprinting process. To optimize the imprinting process and the sensibility, we used optical, SEM and AFM images to evaluate the best imprinting parameters, which are 80 °C and 40 Kg/cm2. Then, we utilized the optimized paper-based sensor to detect gaseous putrescine for monitoring the freshness of salmon. We found a linear relationship between putrescine concentration and the wavelength redshift of the SPR dip. Finally, real samples spiked with putrescine were used to inspect the sensibility of the paper sensor. As a result, we prepare a flexible, eco-friendly and low-cost paper-based sensor for detection in food safety.
In the second part of this thesis, we used the paper-based sensor to detect mercury ions. The mechanism is based on the principle that silver nanoparticles could spontaneously react with mercury ions and consequently form amalgam. The reduction of silver element during the reaction might result in an obvious color change, which could be utilized to determine the concentration of the mercury ions by naked-eye. First, we detect the mercury ions in the nanoparticles’ solution and compare the sensibility of three categories of nanoparticles, which are silver nanoparticles (SNPs), hollow gold nanoparticles (HGNs) and silver-coated hollow gold nanoparticles (HGNs@Ag) toward Hg2+ ions. We found that the SNPs displays the best sensibility and the calibration lines of SNPs and HGNs for Hg2+ ions. Next, SNPs-modified inkjet paper and SNPs-modified PET plate were fabricated for the sensing of Hg2+ ions. We analyze the reflectance and the RGB values to get calibration lines. Due to the reason that the loss in reflectance happen for inkjet paper, we choose PET to prepare the mercury sensor and optimize the fabrication process. Finally, we examine the selective ability of the SNPs-modified PET sensors.
Above all, we fabricate a low-cost, burnable, light and easy-to-use paper-based sensor and it shows great ability to be applied in the food safety and heavy metals detection.

摘要
Abstract
目錄
圖目錄
表目錄
第一章 序論
1.1 研究動機
1.2 論文架構
第二章 文獻回顧
2.1 合金金屬奈米粒子
2.1.1 合成實心金奈米粒子
2.1.2 合成銀奈米粒子
2.1.3 合成中空金奈米粒子
2.2 金屬奈米粒子的光學性質
2.2.1 緒論
2.2.2 表面電漿共振
2.3 金屬奈米粒子於生化感測器領域上的應用
2.4 以紙基材製備生化感測器
2.5 奈米壓印技術
2.6 生物胺與食品安全
2.7 重金屬檢測
第三章 以奈米壓印技術製備低成本紙基感測器及其在食品安全之應用
3.1 研究目的
3.2 研究方法
3.3 結果與討論
3.3.1 奈米壓印製程
3.3.2 以紙基感測器檢測腐胺
3.4 結論
第四章 以奈米壓印技術製備低成本紙基感測器及其在重金屬檢測之應用
4.1 研究目的
4.2 研究方法
4.3 結果與討論
4.3.1 奈米粒子之合成與優化
4.3.2 最佳化汞離子檢測之光譜分析
4.3.3 以紙基感測器檢測汞離子
4.3.4 以PET軟板感測器檢測汞離子
4.3.5 製備PET軟板感測器之參數最佳化
4.3.6 選擇性
4.5 結論
第五章 結論與未來展望
5.1 結論
5.2 未來展望
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