結合鈀金屬之催化性質與二極體元件之微型化優勢，以鈀為氣敏閘極之蕭特基二極體氫氣感測器在微感測應用上相當具有發展潛力。在本論文中，吾人以無電鍍法製備高性能鈀/磷化銦蕭特基二極體作為氫氣感測器，進行鈀膜特性、蕭特基接面品質、電性整流能力、氫氣偵檢表現與氫氣吸附機制之研究分析。另外，將本感測元件與一般傳統蒸鍍所製備之鈀/磷化銦二極體相比較，以評估本感測元件之發展優勢。

　　研究結果顯示，蕭特基接面品質受金屬閘極之鍍膜技術影響甚鉅，且強烈影響元件電性特性、氫氣偵檢表現，甚至氫氣吸附機制。由於無電鍍技術係屬一低溫低能之覆膜製程，經XPS與Raman量測分析發現，以無電鍍法所製備之鈀−磷化銦界面承受較少之應力與缺陷殘存，接面品質優於一般以蒸鍍法所製備者，因此可有效消除蕭特基異質接合之費米能階釘住效應，使無電鍍二極體具備較佳之電性整流特性，擁有較高之啟動電壓與較低之反向漏電流。以熱游離放射模式分析，無電鍍鈀/磷化銦二極體的確具有較高之蕭特基能障值（604 meV）及接合電阻值（340.1 Ohm cm-2），且其接面理想常數（1.01）較接近於1。另外，由SEM觀察可知，無電鍍鈀表面具較高的粗糙度，有利於氫氣檢測響應。

　　另外，本研究以能量觀點出發，首次提出一論點來關聯界面氫原子之能量狀態與其所處蕭特基界面之完美程度。吾人發現，當界面品質愈佳時，其吸附之氫原子擁有較高之能量，根據此一能量論點可以反映界面品質，並提供另一評估蕭特基接合性質之方法。

　　在氫氣感測性能方面，無電鍍二極體對氫氣呈現極佳之感測能力，擁有高靈敏度與寬廣偵檢範圍之特性，與蒸鍍元件相較，其性能更為優越。實驗結果顯示，本無電鍍元件所得氫氣偵檢範圍涵括3個濃度次方以上，其偵檢下限至少低於15 ppm H2/air、上限可達10000 ppm H2/air以上。在暫態響應方面，提高氫氣濃度與操作溫度可大幅增進響應速率，減少吸/脫附所需時間。以393 K下1000 ppm H2/air檢測為例，其響應時間僅需10秒且回復時間亦僅需約1分鐘。
在氫氣感測機制方面，本文提出以氫氣吸附模式來描述感測之機制，並以Langmuir isotherm模式來描述氫氣於此二極體上之吸附行為。由感測時I-V電性關係分析發現，實驗結果與所提模式相吻合，據此可求出平衡時之各項熱力學參數。當操作溫度在303-343 K間，氫氣濃度範圍為50-1000 ppm時，可求出界面吸附反應之 與 分別為–89.2 kJ mol-1與–254.0 J mol-1K-1。另外，本文亦首次提出一解析閘極氫氣吸附座之模式，藉由Temkin isotherm分析發現，無電鍍鈀閘極上擁有較多之氫氣吸附座（約5.271012 m-2），因此較蒸鍍者（吸附座約7.231011 m-2）具較佳之氫氣/偵檢表現。另外，在吸附動力分析方面，吾人可以一階反應方程式成功描述氫氣於此鈀二極體上之初始吸附機制，並進一步求得在333-393 K間之吸附活化能為13.2 kJ mol-1。

　　本研究中亦發現，氧氣對氫氣感測表現之靈敏度與初始響應速率均有明顯之抑制作用。當環境中含氧時，鈀膜上之表面反應愈形複雜，吸附之氧會與氫反應生成OH與H2O而消耗氫原子。因此，在高溫與高氫氣濃度下，二極體之感測靈敏度及初始響應速率會被抑制，且其暫態響應電流會發生異常下降之現象。關於氧涉入之反應機制及暫態響應之分析，尚待進一步探討。

　　綜合以上得知，本文以無電鍍技術可製得高性能之鈀/磷化銦蕭特基二極體，其電性整流性能與氫氣檢測表現均極為優越。文中對於氫氣感測之機制及穩態、暫態之感測行為均獲得良好之解釋。此研究結果已為發展高性能二極體式氫氣感測器奠定良好之基礎，藉此研究亦可提供未來開發多功能感測器之參考。

　In combination of the catalytic property of Pd and the miniaturization advantage of electronic diode, the Pd Schottky diode hydrogen sensors have potentials for micro-sensing applications. In this dissertation, the electroless plating (EP) technique is employed to fabricate the high-performance Pd/InP Schottky diode as a hydrogen sensor. Studies on the EP Pd/InP sensor diode will be focused on the Pd film and Pd-InP interfacial property characterizations, I-V rectifying analysis, hydrogen sensing examination, and detection mechanism investigation. Moreover, the thermal evaporated (TE) Pd/InP diode is also employed for comparative study.

　Experimental results reveal that the junction quality of Pd-InP Schottky interface is strongly dependent upon the metal deposition technique, which can further influence the electric characteristics, hydrogen sensing performances as well as hydrogen adsorption mechanism. From the characterizations of XPS and Raman spectroscopy, it is indicated that the EP diode exhibits the superior interfacial quality with suffering less damages and stress than TE one. With the advantage of low-temperature deposition, the electroless plating can largely reduce the effect of Fermi-level pinning. Therefore, the studied EP diode exhibits the better I-V rectifying properties with higher turn-on voltage and lower reverse leakage currents than TE one. From the analysis of thermionic emission model, the EP Pd/InP diode really possesses the high Schottky barrier height (604 meV) and large contact resistance (340.1 Ohm cm-2). And the ideality factor (1.01) is closer to unity. In addition, from the SEM observation, it finds the EP Pd gate exhibits large roughness, which benefits to hydrogen detections.

　Besides, from the energy point of view, a correlation between the energetic state of interfacial hydrogen adsorbate and the junction quality of Schottky interface is first established. It is found that the hydrogen adsorbed at Schottky interfaces where perfect junction exhibited the higher energy state. This provides an indirect method to evaluate the junction qualities of Schottky interfaces.

　From the hydrogen-sensing performances, the EP Pd/InP diode exhibits the better detection capabilities with larger response, higher sensitivity and wider detectable regime than TE one. Experimental results indicate that the EP diode demonstrates the hydrogen detectable regime approximating more than 3 orders of concentration range less than 15 ppm and up to 10000 ppm H2/air. For transient detections, it is shown the EP diode presents the rapid responses to hydrogen. Both response and recovery rates can be speeded by increasing hydrogen concentration and operating temperature. For the 1000 ppm H2/air detection at 393 K, the EP the response time is only 10 sec, and the recovery time is in 1 minute for EP diode.

　From the hydrogen detection mechanisms, the Langmuir isotherm is employed to describe the hydrogen adsorption on EP Pd/InP Schottky diode. It also provides good correlations between theoretical and experimental results. For hydrogen detection of 50-1000 ppm H2/air at 303-343 K, the and values for hydrogen adsorption at EP Pd-InP interface are determined as –89.2 kJ mol-1 and –254.0 J mol-1K-1, respectively. Moreover, based on Temkin isotherm model, it further finds that EP Pd gate exhibits more available sites (5.271012 m-2) for hydrogen adsorption, which is responsible for its superior sensing performances over TE one (7.231011 m-2). For adsorption kinetic analysis, a 1st-order reaction is found giving good kinetic descriptions to the initial response of EP diode, and the activation energy is obtained as 13.2 kJ mol-1.

　In this work, it further finds the oxygen will strongly hinder the hydrogen detection on sensitivity and response rate. As the detection atmosphere contains oxygen, the surface reactions on Pd become rather complex. With the catalytic property of Pd gate, the oxygen will react with hydrogen for OH and H2O formations and thereby consumes the hydrogen. This will lead to an anomalous current decrease and slow initial response rate, especially at higher hydrogen concentration and higher operating temperature. The hydrogen adsorption involving the reactions with oxygen is needed to be further investigated.
In conclusion, as can be seen, the electroless plating technique can fabricate the Schottky interface with high junction quality for excellent electric rectifying property and hydrogen sensing performances. This study has provided the well investigations into the detection mechanisms as well as steady-state and transient-state hydrogen sensing performances. Based on the high-performance Schottky diode hydrogen sensor, it can be further developed the multi-functional sensor system.

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