本研究係以雙硫醇單分子層修飾金/砷化鎵蕭特基二極體作為氮氧化物感測器，並探討其感測特性。實驗中，首先製備金/砷化鎵蕭特基二極體，接著將元件浸泡入雙硫醇分子之酒精溶液中以修飾其金膜表面。文中改變浸泡實驗變因，例如：浸泡濃度、浸泡時間及硫醇分子結構等因素，並且藉由循環伏安法與接觸角分析來探討單分子層之吸附量、穩定性及表面特性等。其次，改變不同感測條件，包括：氣體濃度、氣體種類及操作溫度來探討元件之感測特性。
在元件之浸泡過程中，雙硫醇分子之吸附量隨著浸泡時間、濃度及碳數而變化；當浸泡溶液之濃度由10μM提升至0.7 mM時，其吸附量隨之增加而達到一穩定值；浸泡時間增加至36小時雙硫醇吸附量達到飽和值；另外，當雙硫醇分子之碳數在3-10間時，隨碳數之增加，則形成之分子膜結構越為穩定，且其吸附量越大。
由一氧化氮與二氧化氮氣體之感測結果可知，硫醇分子之結構對元件之電性與感測能力影響甚鉅。當雙硫醇分子之碳數越高時，其吸附層分子排列愈具自序性、且吸附量越多，因此，表面提供氣體吸附座增加，故感測靈敏度明顯提升。比較-SH、-COOH、-OH、-CH3等不同末端基硫醇單分子層修飾金/砷化鎵蕭特基二極體元件進行感測分析得知，以雙硫醇單分子層修飾具有最佳之感測效果，推測係因其硫醇基與一氧化氮、二氧化氮分別產生亞硝基硫醇(thiolnitrite)、亞硝酸硫醇(thiolnitrate)鍵結之故。亦因如此，故本元件之選擇性高、且不易受背景氣氛之影響。當氮氧化物在1-100 ppm濃度範圍內時，濃度越高時則靈敏度越大；但當操作溫度上升時，則靈敏度下降。
綜合以上結果，烷基雙硫醇單分子層修飾金/砷化鎵蕭特基二極體可作為氮氧化物感測器，其中以癸烷基雙硫醇(HS(CH2)10SH)修飾之元件具有最佳之感測特性。在298 K下，對NO、NO2之靈敏度分別為35.3(100 ppm NO/N2)、49.5(100 ppm NO2/N2)。

In this work, novel nitrogen oxides gases sensors based on Au/GaAs Schottky diodes modified with alkanedithiol monolayers were fabricated and studied. At first, Au/GaAs Schottky diodes were fabricated, and then the Au electrode was modified with alkanedithiol monolayer by immersing the diode in an alkanedithiol/ethanol solution. Experimentally, effects of immersion time, concentration, and structure of alkanedithiol on the adsorption amount, stability, and hydrophobicity of monolayers were investigated by using cyclic voltammetry and contact angel analysis. Moreover, the sensing characteristics of the studied devices on nitrogen oxides were investigated under various gas concentrations and temperatures.
From the result of immersion, the adsorption amounts of alkanedithiol were not only increased with increasing immersing time but also increased with increasing the concentration and carbon number (N) of alkanedithiol. When the alkanedithiol concentration was increased from 10 μm to 0.7 mM, the adsorption amount reached to a monomolecular saturation. As the immersion time approached to 36 hr, the adsorption reached to the equilibrium. Besides, the stability of structure and adsorption amounts of monolayer were increased with increasing carbon number of alkaneditiol in the N range of 3-10.
From results of NO and NO2 sensing performances, the effect of structure of alkanedithiol played great important role on the sensitivity and electric property of the studied device. As the N value increased, the sensitivity of device was consistently increased, since the adsorption amount of monolayer was increased and the molecule architecture tended to self-ordered. As comparing sensing performances among devices modified with different terminal groups, i.e., –SH, -COOH, -OH, and -CH3, it was found that the device modified with alkanedithiol (terminal group: -SH) showed the highest sensitivity. This was inferred that -SH group could form thiolntirite or thiolnitrate by reacting with nitrogen oxide and nitrogen dioxide, respectively. Hence, high selectivity could be obtained, which would not be easily affected by the ambience. Furthermore, the sensitivity of the studied device was increased with increasing the concentration of nitrogen oxides in the range of 1-100ppm. However, the sensitivity was decreased as the operating temperature was increased.
In conclusion, the Au/GaAs Schottky diodes modified with alkanedithiol monolayer had been successfully fabricated and could be served as nitrogen oxides sensors. Among various studied devices, 1,10-decanedithiol modified Au/GaAs device showed the best sensing characteristics on NO and NO2. The sensitivities of this device for sensing NO and NO2 were 35.3(100 ppm NO/N2) and 49.5(100 ppm NO2/N2), respectively, at 298 K.

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