臺灣博碩士論文加值系統

過渡金屬氮化物(MeN)具有優異的耐磨性、高硬度、熱穩定性、良好的導電性及化學穩定性，廣泛使用於切削工具、保護與耐磨塗層(如:TiN、TaN、CrN)，然而熱穩定性溫度卻是有限的，所以添加第三種元素(如: Si、C、Al)來改善抗氧化性，增加高溫穩定性，大量相關研究文獻提到其性質與應用。此對大部分的研究都著重在於機械相關性質，在光學性質與電性方面占少數。
本實驗利用反應式磁控濺鍍製程製備Cr1-xSixN薄膜，探討Si含量對於Cr1-xSixN薄膜光學、電性及高溫熱穩定之影響。使用場發射掃描電子顯微鏡(FE-SEM)、能量散射光譜儀(EDS)、及低掠角X光繞射儀(GIXRD)來觀察薄膜表面、組織結構、化學組成。霍爾量測其薄膜的電性質。使用紫外光/可見光/近紅外光分光光譜儀(UV/VIS/NIR)量測薄膜之穿透率及反射率，並利用穿透率及反射率計算出其吸收率以及透過能隙公式計算其光學能隙。不同Si含量之Cr1-xSixN薄膜分別於大氣中進行300°C~600°C進行熱穩定測試。
實驗結果顯示當Cr1-xSixN薄膜之Si含量的增加，Si在CrN晶格中置換固溶，超出固溶量後，在晶界周圍析出形成a-SiNy，開始覆蓋CrN晶粒導致晶粒縮小。從XRD可觀察到CrN 相繞射峰開始往高角度偏移以及寬化現象，結晶相CrN逐漸被非晶相SiNy覆蓋，表面形貌則由尖錐狀轉變為不規則顆粒狀。Si添加於CrN中，穿透率上升，其性質由金屬轉變為介電質，反射率下降，表面形貌改變導致漫射行為減少。隨著Si含量的增加，其載子濃度下降，導致電阻率上升。薄膜經大氣熱處理後，顯示載子濃度下降，電阻率上升。在大氣退火600°C下，CrN添加Si形成Cr1-xSixN後，相較於CrN，表面形貌發現未完全氧化形成Cr之氧化物，表示添加Si可以改善高溫熱穩定性，而Cr0.76Si0.24N含有最少量的Cr2O3，具有最好的高溫抗氧性。

Transition metal nitride such as TiN, TaN, CrN coatings exhibit excellent wear resistance, high hardness, thermal stability, good conductivity and chemical stability, and is used widely in cutting tools, protective and wear-resistant coating. Related literature points out that addition of Si, C, Al elements can improve their oxidation resistance and increase their thermal stability. Most studies focus on the discussion of mechanical properties, and studies on optical properties and electrical properties are still to be strengthened.
In this study, Cr1-xSixN thin films with different Si contents were prepared by reactive magnetron sputtering, Effectss of the Si content on the optical, electrical properties and high-temperature stability of Cr1-xSixN were investigated. The chemical composition and structure of the studied films were characterized by using the FE-SEM, EDS and GIXRD. Hall Effect Analyzer was used to measure the electrical properties of CrSiN films. The transmittance and reflectance of Cr1-xSixN were measured by using the UV/VIS/NIR. The optical energy gap was calculated from the absorptance by using the energy gap equation. The thermal stability test was carried out at 300 ℃ ~ 600 ℃ in air.
The experimental results show that when the Si content of the Cr1-xSixN film increases, Si displaces solid solution in the CrN lattice. After the solid solution amount is exceeded, a-SiNy is precipitated around the grain boundary, and the CrN grain is covered and then cause the shrinkage of grain. From XRD, it can be observed that the diffraction peak of the CrN phase starts to shift to larger angle and also larger FWHM. The crystalline phase CrN is gradually covered by the amorphous phase SiNy, and the surface morphology changes from a pointed cone to an irregular granular shape. When Si is added to CrN, the transmittance decreases, its properties change from metal to dielectric, reflectivity increases, and chenges in surface morphology cause decreases on diffuse behavior. As Si content increases, the carrier concentration decreases, resulting in increase in resistivity. After atmospheric heat treatment, the concentration of the carrier is decreased and the resistivity is increased. After atmospheric annealing at 600 °C, CrN added Si to form Cr1-xSixN, compared with CrN, the surface morphology was found to be incompletely oxidized to form Cr oxide, indicating that adding Si can improve high temperature thermal stability, while Cr0.76Si0.24N Contains the least amount of Cr2O3, with the best high temperature oxidation resistance.

摘要…………………………………………………………..…………………………...….....i
Abstract…………………………………...……………………..……………………...……...ii
誌謝……………………………………………………………………..………………..……iv
目錄………………………………………………………………………..…………...……....v
表目錄…………………………………………………………………….……………........viii
圖目錄……………………………….….…...……………………….………………………..ix
第一章、 緒論……………………...………………………..……………………….......1
第二章、 文獻探討………………………………………..…………….……………….2
2.1 濺鍍方式………………………………………………..…………..………..…......2
2.1.1 物理氣相沉積………………………………..……………..……..……….....2
2.1.2 電漿特性與形成原理……………………………..……………………….....2
2.1.3 濺鍍系統…………………………………………..……………..……..….....4
2.1.4 直流濺鍍…………………………………………..…………..…….….….....4
2.1.5 射頻濺鍍…………………………………..…………………..….…....…..…5
2.1.6 磁控濺鍍…………………………………..……………………..…..…..…...5
2.1.7 反應式濺鍍…………………………..…………………………..…………...5
2.2 薄膜生長模式………………………………………………………………………6
2.2.1 Volmer-Weber 成長方式…………………..………….....….....……..............6
2.2.2 Frank-van der Merwe 成長方式…………………..………….....….....……...6
2.2.3 Stranski-Krastanov 成長方式………………………..……………...…..……6
2.3 鍍膜材料………………………..……………………..………………..……..……7
2.3.1 氮化鉻……………………..……………………..……………..………..…...7
2.3.2 氮化矽鉻………………..………………………………..…..…………..…...7
2.4 能矽計算………………………………..…………………………..………………7
第三章、 實驗細節…………………..…………..…………………………….……….13
3.1 實驗材料………………………..………………..………………………………..13
3.1.1 靶材…………………………..…………………………………..………….13
3.1.2 基板……………………………...…………….……… ……………………13
3.1.3 化學藥品…………………………..………………………………………...13
3.1.4 氣體……………………………..……………...……………………………13
3.2 基材前處理….……………..……………….……………..………………………13
3.2.1 矽晶片清洗步驟……………………….….….………………..……………13
3.2.2 銅片與玻璃基板清洗步驟…………………..………...……………………14
3.3 實驗製程………………………..………………………………...……………….14
3.3.1 薄膜製備…………………………..…………..…………………………….14
3.3.2 實驗設備……………………………..…..……………………….…………14
3.3.3 熱穩定測試……………………………..…………………..……………….15
3.4 儀器介紹…………………………………..……………………..………….…….15
3.4.1 X光繞射儀……………………………....……………...……….………..…15
3.4.2 場發射電子顯微鏡與能量散射光譜儀.......................…………………..…15
3.4.3 紫外光/可見光/近紅外光光譜儀..…………………...……….……………16
3.4.4霍爾量測儀…………………………………………………………………..16
3.5薄膜分析………………………………..…………………...…...………………...16
第四章、 結果與討論…………………………..……………….………..….…………21
4.1 探討Si含量對Cr1-xSixN薄膜結構、光學與電性質之影響.…………………......21
4.1.1 Cr1-xSixN薄膜之製備…………….……………..…………………...…..…..21
4.1.2 Si含量對於Cr1-xSixN薄膜結構影響………….……………………………23
4.1.3 Si含量對於Cr1-xSixN薄膜之光學性質影響…….…………………..…..…26
4.1.4 Si含量對於Cr1-xSixN薄膜之電性質影響……….………………..……..…30
4.2 不同Cr1-xSixN薄膜之大氣熱穩定性能探討…………………………..…..…….32
第五章、 結論………………………………………………..…………………...….…50
參考文獻……………………………………………………………..………………..….…..51
Extended Abstract…………………………………………………..…………………..……54

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