Please use this identifier to cite or link to this item: http://hdl.handle.net/11455/9824
標題: Synthesis and Characterization of Metal-Containing and Hydrogenated Diamond-Like Carbon Films Deposited by Unbalanced Magnetron Sputtering Process
非平衡磁控濺射沉積含金屬類鑽碳膜之特性研究
作者: 張奇龍
Chang, Chi-Lung
關鍵字: 非平衡磁控濺射;Unbalanced Magnetron Sputtering (UBM);類鑽碳膜;光學發射光譜儀;金屬電漿離子植入;多層膜;Diamondlike Carbon Film (DLC);Optical Emission Monitor (OEM);Metal Plasma Ion Implantation (MPII);Metal Vapor Vacuum Arc Plasma Ion Implantation (MEVVA);Mutillayer
出版社: 材料工程學研究所
摘要: 
本研究主要是利用非平衡磁控濺射系統發展一套新的類鑽碳膜沉積製程並尋求解決附著力之方法,以及對其基本性質作一探討。
本研究成功的沉積一含氫及鈦金屬之類鑽碳膜於工具鋼、粉末冶金等基材上,並藉由連續式沉積鈦、氮化鈦、氮碳化鈦之中介層作為改善類鑽碳膜附著力不佳之問題。在這製程中我們分別使用N2、C2H2作為氮與碳的來源,並以Optical Emission Monitor(OEM)作為反應氣體濃度的控制元件,再藉由鈦金屬電漿轟擊以解離N2、C2H2氣體,而反應形成鈦、氮化鈦、氮碳化鈦之中介層及類鑽碳膜的沉積,其厚度控制可由0.1μm到5μm或更厚。
本研究所沉積之類鑽碳膜之性質主要受OEM Setting、Substrate Bias以及介層設計參數所影響。在鈦、氮化鈦、氮碳化鈦之中介層設計下可以得到最佳的附著力與磨耗壽命,其附著力可由25N提升至70N且磨耗壽命亦提升2至3倍以上。而在低OEM Setting與高Substrate Bias下可以得到較高的硬度與良好的磨潤性質,但過高的Substrate Bias所產生的高內應力卻不利於鍍膜的附著性與磨耗壽命,其硬度依製程參數變化約在15到30GPa或更高。在磨耗測試中,以WC球為對磨材量測其摩擦係數發現,其在不同環境下具有不同的摩擦係數,在大氣氣氛下約維持在0.07至0.1,而在水溶液下則為0.2。此差異主要來自於石墨化轉移層磨耗機制受水溶液沖蝕所致。在抗氧化能力上則以TGA量測,並得到其抗氧化溫度約為350℃。
另外,並以MEVVA系統植入高能量之碳、鈦離子至類鑽碳膜表面發現,其硬度值明顯下降,經Raman、XPS以及TEM分析後發現,隨著值入能量愈大其sp3鍵結比例愈低,顯示類鑽碳膜在受高能量離子植入與轟擊下對原有sp3鍵結形成破斷的效應,而趨向形成較穩定之sp2鍵結,因此導致類鑽碳膜硬度值的下降。但在碳離子植入TiN薄膜的研究中,我們發現其硬度值明顯上升,經XRD、XPS以及TEM分析後發現,隨著值入能量愈大其形成二元與三元的反應物愈多,加上未反應而形固溶強化的相乘效應,而導致薄膜硬度的明顯提升。結果反應在摩擦係數下降至0.2,且耐磨耗壽命亦延長。
最後,本研究所發展之含複層介面之連續、單一製程的含氫與金屬之類鑽碳膜設計,已成功的運用於各種的IC封裝與粉末冶金成型模具上,並有效提升其模具的使用壽命達二倍以上。

The research purpose was to develop a new process and improve adhesion of diamond-like carbon films. In this study, an amorphous hydrogenated diamond-like carbon coating containing a small amount of titanium, and exhibiting high hardness, low friction coefficient, and superior adhesion strength, were successfully deposited onto M2 tool steel substrate using closed-field unbalanced magnetron sputtering (CFUBM) techniques. In DLC synthesized, an important role from changing the concentration of C2H2 can be controlled by a closed-loop optical emission monitor (OEM). The component, not only to regulate the reactive sputtering of metal and metal nitride/carbide interlayer, but also to control the amount of metal inclusion in the final DLC deposition. With the decrease of OEM settings, corresponding to a lower friction coefficient, longer wear life, higher microhardness and residual stress. The phase transformation from TiC to DLC is strongly influenced by OEM settings, and is demarcated on the OEM setting of 20%.
An interface layer of Ti/TiN and a transition layer of TiCxNy were incorporated to provide a supportive foundation for DLC and to solve the adhesion problem between DLC and steel substrates. These interfaces already improve the adhesion from 25 to 70 N between the DLC coating and the substrate. The total thickness of the DLC coatings can be controlled between 0.1 to 5 μm or higher. The DLC coatings showed excellent properties, i.e. high microhardness value (between 15 to 30 GPa or more), low friction coefficient against an WC and 52100 steel ball being in the range 0.07 to 0.2 in air, depended on the hardness of DLC coatings by OEM setting values.
The TGA analysis indicates the DLC films disintegrated at 350℃, showing typical graphitic transformation and oxidation behavior.
For ion implantation DLC coatings, the microhardness and the sp3/sp2 ratio evidently decreased from 16.2 to 11.6 GPa and 0.46 to 0.30, respectively, as ion energy increased. Results from damage by breaking some of the film's sp3 bonds due to high-energy ion bombardment.
For the implantation of carbon in TiN coatings, the microhardness increases from 16.8 to 25.3 GPa, and new microcrystalline phases of TiCN and TiC are formed, depending on the implanted ion energy and dose. These newly formed microcrystalline phases can enhance the microhardness and reduce the wear of TiN films.
Final, this new model DLC process was successfully developed, including multi-interface and combined PVD/ PECVD process, using closed-field unbalanced magnetron sputtering technique.
URI: http://hdl.handle.net/11455/9824
Appears in Collections:材料科學與工程學系

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