以反應性直流磁控濺鍍製備氮化鉻硼鎢奈米複合薄膜之製程與性質研究

The synthesis and performance of Nanocomposties Cr-B-W-N Coatings by Reactive DC Magnetron Sputtering

曾麟詠(Lin-Yung Tseng)

指導教授 ： 徐開鴻 ； 張奇龍

國立臺北科技大學/工程學院/材料科學與工程研究所/碩士(2011年)

https://doi.org/10.6841/NTUT.2011.00188

摘要

本研究使用反應性直流磁控濺鍍系統製程氮化鉻硼鎢(Cr-B-W-N)奈米複合薄膜沉積於(100)矽晶片、碳化鎢及不銹鋼片基材上，主要以鎢靶材功率作為變化參數，探討對於氮化鉻硼鎢奈米複合薄膜的微結構、機械性質、腐蝕性質與高溫氧化性質之影響。利用掃描式電子顯微鏡(SEM)、穿透式電子顯微鏡(TEM)、原子力顯微鏡(AFM)及X光繞射儀(XRD)觀察氮化鉻硼鎢奈米複合薄膜之微結構、晶粒大小及殘留應力的變化，元素成份之組成分析與膜層設計之縱深變化使用化學分析電子光譜儀(ESCA)及輝光放電分光儀(GDS)，機械性質則使用奈米壓痕來測定薄膜硬度與楊氏模數，再以恆電位儀、四點探針及水接觸角來檢測薄膜的抗腐蝕特性、電性變化與親/疏水特性。
實驗結果顯示，隨著鎢靶材功率的增加，氮化鉻硼鎢(Cr-B-W-N)薄膜組成的鎢元素含量會隨之增加，而鉻元素及硼元素則相對被抑制而降低，造成薄膜不同化學計量比的變化，薄膜微結構由非晶氮化硼BN相和氮化鉻鎢(Cr, W)N奈米晶粒所組成，並含有少量的氧化物。BN相及CrN相的體積分率減少，相對W2N的體積分率增加，使薄膜硬度範圍在12~19GPa，介於氮化鉻硼(Cr-B-N)、氮化鎢(W-N)薄膜的硬度值16GPa及24GPa；電阻值會由321.6μΩ-cm下降至260.5μΩ-cm；表面親水特性越趨明顯；在3.5wt.%NaCl水溶液中，腐蝕性質劣於氮化鉻硼(Cr-B-N)薄膜。
從結果可知薄膜微結構、機械性質、物理與化學特性，會因組成元素比例的不同而有所差異，主要決定於BN、CrN與W2N的組成體積分率有關，隨BN、CrN的體積分率下降，導致耐蝕性變差，表面特性不利於模具之脫膜性，而W2N的組成體積分率增加，提升了薄膜硬度值。

關鍵字

直流磁控濺鍍 ； 氮化鉻硼鎢 ； 奈米複合薄膜

並列摘要

Nanocomposite Cr-Al-Si-N films have been deposited on Si wafer, tungsten carbide and stainless steel substrates by reactive DC magnetron sputtering. The influences of tungsten target power on the synthesis, microstructure, mechanical, corrosion, and high temperature oxidation properties of the Cr-B-W-N films were investigated. Scanning electron microscopy, transmission electron microscopy, X-ray diffraction techniques were also employed respectively to analyses the microstructure, grain size and residual stress. The chemical composition and depth analyses of the deposited Cr-B-W-N coatings was evaluated using electron spectroscopy for
chemical analysis and glow discharge spectrometer. Nano-indentation were used to measure the microhardness of Cr-Al-Si-N thin films. The experimental results indicate that the Cr-B-W-N coatings exhibit a nanocomposite structure of nanocrystalline (Cr,W)N, a soft amorphous BN matrix and a small quantity of oxides. Decrease BN amorphous matrix volume fraction and CrN volume fraction, increase W2N volume fraction in Cr-B-W-N films, subsequent results showed that the hardness of the films ranged from 12-19GPa, which were between the CrBN (16GPa) and WN (24GPa) thin film, with increasing tungsten target power. Increase in the surface roughness leading to a decrease in the contact angle was related to a decrease in the BN amorphous matrix volume fraction and CrN volume fraction in Cr-B-W-N films. The corrosion resistance of coatings was investigated in 3.5wt.% NaCl aqueous solution by means of an electrochemical potentiodynamic polarization. The results showed that the corrosion resistance of Cr-B-W-N coatings was deteriorated than that CrBN coatings. It was found that the microstructure, mechanical, physical and chemical properties of the films correlated with W concentration , and amorphous BN, CrN and W2N volume fraction. With the BN and CrN volume fraction decline, relatively the W2N volume fraction increases, was created deterioration of the corrosion resistance, and surface properties was not conducive to demoulding performance. The composition of the W2N volume fraction increases, enhancing the film hardness.

並列關鍵字

DC magnetron sputtering ； Cr-B-W-N ； nanocomposties Ccatings

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