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清華大學材料科學工程學系學位論文

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  • 學位論文

自離子感測場效電晶體(ISFET)發明以來,在氧化物及氮化物感測膜上已有很廣泛的研究,此外,更進一步發展出延伸式閘極離子感測場效電晶體(EGFET),此結構能防止水溶液侵入電晶體閘極(Gate),並能更專注於感測薄膜的開發,也易於改變感測薄膜的形狀。而由於閘極為延伸式感測薄膜,故更需低阻抗、導電率高的薄膜。 本論文在ITO表面上使用水熱法鍍 CuInS2硫化膜,以不同溫度退火下的薄膜作為感測薄膜應用在延伸式閘極離子感測場效電晶體,針對 pH 值、銅離子、銀離子、鉛離子,測量其對離子感應的靈敏度。 本論文得知,500。C退火CuInS2薄膜,對各種離子靈敏度最佳,對氫離子可達56.2 mV/pH,對銅離子可達44.8 mV/pCu,對銀離子可達51.2 mV/pAg,對鉛離子可達39.7 mV/pPb,線性相關係數皆可達0.938以上。 本論文將使用兩種不同的EGFET作業方式,分別為 N-type MOSFET-EGFET Linear Mode以及N-type MOSFET-EGFET Saturation Mode,取得其對應的靈敏度,期望能得知感測薄膜帶在VG或VT改變的影響,並藉由量測I-V的特性來推斷 CuInS2 對離子的感測靈敏度,同時也將薄膜作物理性質分析,包括XRD分析、SEM分析、EDX分析、ESCA分析。

  • 學位論文

金屬有機骨架化合物,尤其是MOF-5,作為一種新型的孔洞材料,被視為是極具有潛力的儲氫材料。MOF-5在氣體的吸附與儲存上具有極大的潛力,主要是因為它具有很大的比表面積、很大的孔洞量以及很好的熱穩定性。在本實驗中,我們以二價鹼土金屬陽離子(Mg2+, Ca2+) 以及過渡金屬陽離子(Cu2+) 摻雜改質MOF-5儲氫基材,並研究其儲氫性質。 從實驗結果我們發現,當少量摻雜Mg2+離子時,其可以些微的增加氫氣吸附量至3.0wt%,而當過量摻雜Mg2+離子時則會降低MOF-5的氫氣吸附量。另外,摻雜Ca2+ 或 Cu2+離子時皆會使得MOF-5的氫氣吸附量降低。 我們認為,當摻雜Mg2+或Ca2+離子時,其會與MOF-5骨架金屬節點中的Zn2+發生置換,而這樣的置換會些微的破壞MOF-5結構,而導致其比表面積降低,使得其氫氣吸附量也降低。然而,Mg2+離子的置換可以增加MOF-5骨架與氫氣間的交互作用力;而其輕金屬中心的效應也有助於直接提升MOF-5的氫氣吸附量。 另外,Cu2+離子並不能與MOF-5骨架金屬節點中的Zn2+離子發生置換,而是以Cu(CH3COO)2 或是 CuO等形式卡在MOF-5的孔洞骨架之中。因而導致其比表面積降低,使得其氫氣吸附量也降低。

  • 學位論文

Diabetes mellitus, commonly known as Diabetes is a group of metabolic diseases in which a person has high blood sugar, either because the body does not produce enough insulin, or because cells do not respond to the insulin that is produced. Diabetes is a major health problem worldwide in the world we know today. The management of diabetes requires extensive monitoring of blood sugar (glucose) over a long period of time. This in turn requires large numbers of testing, hence the accuracy and price of every test is a common concern. In this work we look into the feasibility of compact, economical extended field effect transistor (EGFET) glucose sensors made by inexpensive electrodeposition method. Sensing films for EGFET were fabricated using ZnO nanorods using a three electrode electrodeposition method and then coated with immobilized glucose oxidase enzyme. Different morphologies and crystalinity of ZnO nanorods were examined to find the optimum sensitivity to glucose concentration variations. Samples of nanorod arrays with diameter ranging from 50~500nm were fabricated, the samples are checked for morphology and crystallinity via scanning electron microscope and X-ray diffraction, the sample is also checked for impurities using energy-dispersive X-ray spectroscopy . Glucose oxidase are then immobilized on the nanorod array and connected to the gate of a commercial MOSFET to perform the glucose concentration sensing. Most samples exhibit a sensing limitation down to approximately 10-8 mole, in which some achieve sensitivity of up to 7.8 μA/p[g]. The reaction time of the sensing film is dependent on the amount of enzyme immobilized; reaction time of fewer than 20 second can be achieved. The sensitivity of the EGFET is found to be highly correlated to the morphology of the nanorod array, decrease in nanorod diameter resulted in the increase in sensitivity. In addition, samples with moderate crystalinity show better sensitivity; this may be due to excess dangling bonds in which defects expose to the surface. Thus causing more sites for the bonding of H+ , which can be seen as having a higher capacity for the sensing of glucose. However the nature of nanorods with too small diameter proves to be poor in crystalinity, this causes the in loss conductivity, which inevitably lead to the loss of sensing signal.

  • 學位論文

本研究在鈦酸鋇粉體表面被覆高分子作為粉體成長的抑制劑,使粉體在高溫過程中凝團成長受到抑制,並透過空氣及氮氣的切換控制抑制劑的殘存量,達到粒徑大小的控制。研究結果顯示,在高溫熱處理下,鈦酸鋇粉體粒徑會隨著高分子被覆量的增加而變小;同時,透過X光繞射圖譜及拉曼光譜的分析結果顯示,粉體的正方性會隨著粒徑的變小而下降。並利用阻抗頻譜模擬分析與熱差分析儀證實粉體的介電常數及居禮溫度也會隨著粒徑的變小而下降。最後將1000oC下被覆2.5wt% PAA-NH4之鈦酸鋇粉體進行濕式球磨法,在不改變其正方性的狀態下使粉體粒徑下降。

  • 學位論文

本研究利用有機化學法合成均質的Ce0.8-YGd0.2-XCaXCoYO1.9-δ 乾燥凝膠錯合物,由於參與反應的金屬離子能緊密接鄰,因此經過700°C 煆燒熱處理後,即可生成單一純相Ce0.8-YGd0.2-XCaXCoYO1.9-δ 粉體結晶相,實驗結果得知添加3mol% 鈷(Y = 0.03)以及10mol% 鈣(X = 0.1)可以得到最佳導電度,該煆燒粉體經過1000°C 燒結熱處理後即能緻密,且相對燒結緻密度可達95%以上。實驗結果確定鈣取代量為10mol%為最佳,在700oC下導電率達0.046Scm-1,其原因為鈣離子之離子半徑大於鈰及釓離子,鈣離子進入氧化鈰之晶格中將其晶格撐開而提升載子移動率連帶地增加導電率。

  • 學位論文

銅奈米尺寸雙晶(nanotwin)結構能大幅提升機械強度以及擁有良好的導電性,因此銅奈米雙晶結構被視為未來半導體製程中內連結導線的候選者之一。然而在文獻中有關於銅奈米雙晶導線氧化方面的資訊缺乏,因此本論文致力於研究銅奈米晶的氧化特性,本研究利用即時電性量測銅薄膜試片,並觀察在不同時期銅薄膜的氧化現象,並討論銅氧化的動力學機制。 本研究最主要的目的是,了解銅薄膜中引入奈米雙晶結構對於銅氧化特性的影響。利用電子槍蒸鍍(E-gun)來製備銅薄膜試片,並於200°C氧化氣氛下持溫,並觀察其氧化情形。首先利用不同鍍膜速率以及鍍膜溫度,製備不同密度的銅奈米雙晶薄膜試片,藉由TEM的分析來確認試片結構,發現高鍍膜速率銅膜擁有較高密度的奈米雙晶結構;此外,本實驗也利用AFM觀察不同時期的氧化形貌,觀察到高鍍膜速率銅膜表面粗糙度較小;利用XRD分析試片,結果顯示:四種試片的氧化物都是生成氧化亞銅,並無氧化銅的相生成;利用SEM從微結構的觀點,高鍍膜速率銅膜氧化過後,氧化層所形成的孔洞以及缺陷較少,由於擁有奈米雙晶的銅膜表面較為平整,因此形成氧化物較小分布也較均勻;利用電性量測方法量測試片在不同溫度下持溫,其電阻值變化與溫度、時間之間的關係,研究發現,高鍍膜速率銅膜氧化速率較低,此外,分析其氧化曲線可以得知:在高鍍膜速率中,主要的氧化機制由擴散所控制,由此可以推論引入奈米雙晶結構之後銅膜的氧化機制傾向以擴散控制為主,由此可以推論奈米雙晶結構扮演著降低氧化速率的角色,因此引入奈米雙晶結構的銅膜可以有效降低氧化速率。

  • 學位論文

摘要 本實驗藉由第一原理分析CoSi(核)/SiO2(殼)、CrSi2 (核)/SiO2 (殼)和 FeSi(核)/SiO2 (殼)奈米電纜異常的鐵磁性質,這是有別於它們在塊材時為反磁性以及順磁性材料的。這樣的奈米電纜結構,主要是因為表面的過渡金屬原子未完全配位鍵結及鍵結的扭曲,使得過渡金屬原子3d軌域的自旋向上和自旋向下的電子數不同,而有鐵磁性材料的性質。藉由高解析度電子顯微鏡圖來確定其成長方向和朝向界面的方向,以朝向界面的方向的過渡金屬矽化物和非晶質SiO2接合,建構近似真實奈米電纜的表面結構,並利用第一原理模擬分析。CoSi奈米線為B20型態結構(空間族為P213),其沿著[211]方向成長,CoSi奈米線除了表面鍵結得不對稱性產生磁性外,內部的缺陷也會產生磁化量,藉由近一步的缺陷假設計算,將內部缺陷產生的磁化量分配到表面Co原子,計算結果和實驗結果相近; CrSi2奈米線為C40型態結構(空間族為P6222),其沿著[0001]方向成長,CrSi2奈米線磁化量來自於表面不對稱鍵結,第一原理計算出的值在加上表面粗糙度所增加的表面積以及氧的影響,計算結果得出和實驗結果相同數量級的磁化量;FeSi奈米線為B20型態結構(空間族為P213),其沿著[111]方向成長FeSi奈米線磁化量也是來自於表面不對稱鍵結,由於上下界面Fe原子距離表面差異大,使的磁化量差距大。了解過渡金屬矽化物奈米線的磁性來源,可以研究其在磁性半導體的應用。

  • 學位論文

A new process to produce rapidly a two-layer (Ni3P/Cu) structure as front-side conductor of textured mono-crystalline silicon solar cells has been developed. This new technique combines microcontact printing with electrochemical deposition. Microcontact printing is a simple and cost-effective method to create selective emitter patterns on silicon-based solar cells. Electrochemical depositions, including both electroless deposition of amorphous nickel–phosphorus (NiP) and electroplated copper (Cu), offer a low-cost process relative to the conventional silver-paste technology. The first step is to imprint Pd ink on the front side of solar cells by microcontact printing, which provides an activation layer. The second step is electroless deposition of NiP film. After annealing the NiP film at 400 ˚C in N2 furnace for ten min, Cu layer is deposited to increase line conductivity. A NiSi phase is formed between the NiP film and silicon substrate. The crystallization of amorphous NiP film was confirmed by an increase in Ni3P peaks in XRD spectra. The contacts formed on Si in the as-deposited NiP films are ohmic with a contact resistivity of about 10−4 Ωcm2. which is better than the conventional silver-paste contacts (10−3 Ωcm2). The width of finger by microcontact printing is less than 40 μm. Furthermore, the substrates being lightly POCl3 doped with a sheet resistance of 80 Ω/ gain in short-wavelength response and decrease the surface recombination, contact resistance, surface recombination velocity as well as emitter area, thus resulting in improved performance of cells. Microimprinting can increase not only cell efficiency but also module power. Compared with conventional solar cell without antireflection coating, the improvement in solar cell efficiency by more than ~1% can be achieved. The results indicate that this technique has potential applications in solar cell fabrication.

  • 學位論文

本實驗使用溶膠凝膠法(Sol-gel method),製備複鐵式鐵酸鉍薄膜(BiFeO3)。在當前BFO薄膜研究文獻中,報導其在室溫下具有較低的漏電阻抗性,使其在研究與應用方面皆遭受限制。因此在本篇論文探討摻雜稀土元素鈰Ce進入BFO薄膜,藉由具有四價及三價的鈰離子取代鉍離子來改善薄膜的漏電流問題;再將具有Ce摻雜的Bi1.05-xCexFeO3薄膜與BiFeO3薄膜作複合層結構,以及另一部分為加入一層氧化鈰的緩衝層在Pt底電極與薄膜之間,分別探討薄膜結晶結構與鐵電、鐵磁性質間的關係。 由實驗結果可得知,Ce的摻雜、複合層結構、氧化鈰緩衝層皆具有改善薄膜漏電流密度影響的效果,量測所得值約介於10-8至10-6 A/cm2之間,其中複合層結構具有減緩接近高電場時漏電急遽上升的現象;根據電場-電流密度圖形分析,薄膜漏電機制應為Space charge limited conduction的導電機制。在電滯曲線圖形上,夾心結構BCFO/BFO/BCFO(1/4/1)與BFO/BCFO(8/1) 550˚C退火試片呈現似飽和電滯曲線的形狀,並且BFO/BCFO(8/1) 550˚C 此組試片,在外加電場200kV/cm下所得2Pr值可達13.80μC/cm2,此較佳鐵電特性可能與較低漏電流有關。而加入緩衝層可使純BFO薄膜極化量微幅增加, 2Ec值下降。

  • 學位論文

Multiferroic material is a subject of increasing interest recently. Not only because BiFeO3, with high Curie temperature (TC = 810-830℃) and Neel temperature (TN = 370℃), is one of the multiferroic material, but also because there is another phase, Bi2Fe4O9, exists that has variety of applications. In the present work, the syntheses, characterization, and study of optical properties of single-crystalline BiFeO3 and Bi2Fe4O9 have been done. The two ternary bismuth ferrite compounds can be obtained by conventional hydrothermal method with simple experimental procedure. Besides, the experimental results illustrate that Bi2Fe4O9 with different morphologies can be exactly controlled by adding ethylenediamine as surfactant or by controlling the molar ratio of potassium ions and sodium ions (K+/Na+). Optical absorption properties were confirmed by UV-Vis. The energy band gap of Bi2Fe4O9 is in the visible light-region. Therefore, it has the potential application to be one of the good candidates for visible-light photocatalyst. Moreover, Bi2Fe4O9 has also attracted much attention because of the possible application in photodegredation. In our experiment, we optimize the experimental procedure and provide a simple way to synthesize and growth pure single-crystalline BFO and Bi2Fe4O9 submicron particles with different morphologies.