臺灣博碩士論文加值系統

本研究利用陰極電弧沉積系統沉積鈦鈮鋯鉭(TiNbZrTa)合金氮化物薄膜，藉由改變氮氣(N2)與氬氣(Ar)的氣體流量比，沉積無通入氮氣的純合金TiNbZrTa、加入微量(10%)氮氣的TiNbZrTaN0.27及氮氣流量佔90%的TiNbZrTaN等三組薄膜，薄膜的製程使用鈦鈮合金靶(TiNb)、純鉭靶(Ta)和純鋯靶(Zr)來沉積鈦鈮鋯鉭(TiNbZrTa)合金薄膜及不同氮含量之鈦鈮鋯鉭(TiNbZrTa)合金氮化物薄膜，鍍膜設計以TiNb做為介層用來提升基材與頂層的鈦鈮鋯鉭(TiNbZrTa)合金氮化物層間的附著性。鍍製試片先以洛式壓痕測試(Rockwell hardness test)確認薄膜與基材間的附著性能達到需求後，送入快速退火爐(RTA)進行快速熱退火氧化試驗。高溫氧化試驗中的加熱溫度分為400°C、600°C與800°C三種溫度，達到指定溫度後將試片持溫於空氣中60分鐘，最後再觀察經過高溫氧化退火後薄膜微觀結構與機械性質上的改變。
本研究透過高解析度場發式掃描電子顯微鏡(Field-emission scanning electron microscope, FESEM)並搭配X光能量分散光譜分析儀(Energy-dispersive X-ray spectroscopy, EDS) 分析薄膜截面的微觀結構及氧化層厚度；採用X光繞射分析儀(X-ray Diffractometer ,XRD)分析薄膜鍵結與高溫氧化後的晶相變化，最後再使用X光光電子能譜儀(X-ray photoelectron spectroscopy , XPS)檢測經過不同溫度的高溫氧化後化學鍵與氧化深度的變化。機械性質的量測以洛式壓痕測試(Rockwell hardness test)獲得薄膜與基材間的附著性，薄膜表面性質使用三維表面輪廓儀(3D surface profilometer)檢測表面平均粗糙度、四點探針系統(Four Point Measurement System)量測薄膜電阻值、最後使用水接觸角量測儀(Water Contact Angle, WCA)分析親疏水性能，再以微小硬度試驗機(Vickers Hardness Test)檢測出薄膜的硬度。
實驗結果顯示TiNbZrTaN薄膜在400˚C快速熱退火後具疏水性及高硬度(3194 Hv)，顯示此薄膜有良好抗沾粘性及機械性質及，但在600˚C以上的高溫環境穩定性較差，其機械性能會大幅衰退，較適合應用於400˚C內的非連續性切削加工。
TiNbZrTaN0.27在經過600˚C快速熱退火後薄膜硬度為1563 Hv且為親水性，適合細胞生存，由於選用的元素Ti、Nb、Zr與Ta都是優良的生醫級金屬，能提供理想的生物相容性減少對人體的傷害，希望能應用於生醫植體。

In this study, TiNbZrTaN0.27 coatings with different nitrogen contents were synthesized by cathodic-arc evaporation(CAE). TiNb alloy, Zr and Ta target material cathodes were used for the deposition of TiNbZrTaN0.27 coatings. During the coating process of TiNbZrTaN0.27, different nitrogen gas flow rate ratio to Ar of 0%,10% and 90% were deposited. TiNb was deposited as an interlayer to enhance the adhesion. After deposition, the three kinds of TiNbZrTa coatings were treated by rapid thermal anneaing (RTA) at high temperature of up to 400˚C,600˚C and 800˚C in air to investigate their mechanical properties caused by rapid high temperature oxidation.
The microstructure and chemical composition of the deposited and RTA treated coatings were investigated by field emission scanning electron microscope (FESEM) and X-ray diffraction (XRD), equipped with an energy-dispersive x-ray analysis spectrometer (EDS). X-ray photoelectron spectroscope (XPS) was used to measure the oxidation scale and chemical bond of the deposited coatings after RTA. Mechanical properties, such as the hardness, were measured by means of micro vickers. A 3D surface profilometer was used to meaure the surface roughness. A Four point measurement system was used to meaure the sheet resistance. Water contact angle (WCA) test was used to evaluate the surface hydrophobility.
The experimental results show that TiNbZrTaN film has hydrophobicity and high hardness (3194 Hv) after rapid thermal annealing at 400˚C, which shows that the film has good adhesion resistance and mechanical properties, but the high temperature environment stability above 600˚C is poor. Its mechanical properties will decline sharply, so it is more suitable for discontinuous cutting within 400˚C. TiNbZrTaN0.27 has a film hardness of 1563 Hv after rapid thermal annealing at 600˚C and is hydrophilic, suitable for cell survival, Because the selected elements Ti,Nb,Zr and Ta are all excellent metals used for biomedical, they can provide ideal its biocompatibility reduces harm to the human body, and is more suitable for biomedical implants.

摘要.....i
Abstract.....ii
誌謝.....iv
目錄.....v
表目錄.....ix
圖目錄.....x
第一章 緒論.....1
1.1 前言.....1
1.2 研究動機和目的.....2
第二章 文獻回顧.....3
2.1陰極電弧沉積系統(Cathodic arc evaporation, CAE).....3
2.2 薄膜成長機制.....4
2.3 重要生醫級金屬與合金介紹.....5
2.3.1鈦(Titaniun).....5
2.3.2鈮(Niobium).....6
2.3.3鋯(Zirconium).....8
2.3.4鉭(Tantalum).....8
2.3.5五氧化二鉭(Ta2O5).....10
2.3.6鈦鈮鋯鉭多元合金.....11
2.4快速真空退火系統.....16
2.4.1快速真空退火系統原理.....16
2.4.2快速真空退火運作特性.....16
2.4.3快速真空退火系統的優點.....17
2.5氮氣流量比對氮化物薄膜的影響.....18
第三章 實驗方法.....20
3.1 實驗流程.....20
3.2 薄膜設計與實驗方法.....21
3.2.1 前處理及鍍膜步驟.....21
3.2.2 純合金TiNbZrTa薄膜製程設計.....23
3.2.3 TiNbZrTaN0.27/ TiNbZrTaN薄膜製程設計.....24
3.3 快速真空退火系統(Rapid Thermal Anneaing System).....25
3.4 薄膜微結構及成份分析.....26
3.4.1 場發射掃描式電子顯微鏡(Field Emission Scanning Electron Microscope, FESEM).....26
3.4.2 X光光電子能譜儀(X-ray photoelectron spectroscopy , XPS).....28
3.4.3 X光繞射分析儀(X-Ray Diffractometer, XRD).....29
3.5 薄膜表面性能分析.....31
3.5.1 三維表面輪廓儀(3D Surface Profilometer).....31
3.5.2 水接觸角量測儀(Water Contact Angle, WCA).....32
3.5.3 四點探針量測系統(Four Point Measurement System).....34
3.6 薄膜機械性質分析.....36
3.6.1 洛氏壓痕試驗(Rockwell Indentation).....36
3.6.2 維克氏硬度試驗機(Vickers Indentation).....37
第四章 結果與討論.....38
4.1 薄膜微結構分析.....38
4.1.1 FESEM薄膜截面形貌分析.....38
4.1.2 FESEM表面形貌及EDS元素成份分析.....46
4.1.3 X光繞射分析.....50
4.1.4 XPS鍵結態分析.....57
4.2 薄膜表面性質分析.....61
4.2.1表面粗糙度分析.....61
4.2.2親疏水性能分析.....66
4.2.3薄膜電阻分析.....70
4.3 薄膜機械性能分析.....71
4.3.1洛式硬度分析.....71
4.3.2維克氏硬度分析.....72
第五章 結論.....75
參考文獻.....77
Extended Abstract.....83

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