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Preparation of chromium oxynitride thin films by physical vapor deposition using air as a reactive gas
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過去文獻利用物理氣相沉積法 (Phsical Vapor Deposition, PVD) 製備CrNxOy薄膜時，都會將腔體抽至低的背景壓力(高真空)，避免殘存的空氣對薄膜造成影響，在抽除腔體氣體時，通常需耗費長時間使製程成本提高，近年來，全球經濟衰退，環保議題也備受重視，本研究希望在高背景壓力下(1.3×10-2 Pa)通入空氣反應性氣體以製備出CrNxOy薄膜，藉此縮短製程抽真空所需耗費的時間，達到節能環保、降低製程與原料成本的目的。
本研究主要利用PVD在不同背景壓力下(1.3×10-2 Pa、6.6×10-4 Pa)以空氣作為反應性氣體製備CrNxOy薄膜，控制air/Ar流量比值在(0~46)/100，鍍著功率200 W、偏壓-50 V、工作壓力0.19~0.20 Pa、鍍著時間20 min下所鍍著之薄膜，分別以X光繞射儀 (XRD) 分析所鍍著薄膜之結晶結構，以場發射掃描式電子顯微鏡 (FE-SEM) 觀察薄膜微結構，以歐傑電子能譜儀 (AES) 及X光光電子能譜儀 (XPS) 進行薄膜深縱分析及成分分析，以四點探針 (Four point probe) 量測薄膜導電性，以奈米壓痕儀 (nano-indenter) 量測薄膜硬度，以雷射曲率法 (Scanning laser curvature)量測薄膜殘留應力，最後綜合各儀器分析結果歸納出CrNxOy薄膜的性質。在高背景壓力(1.3×10-2 Pa)下，所製備之薄膜在air/Ar流量比值30~33/100時，薄膜晶體結構為岩鹽結構，橫截面為柱狀晶結構，氧含量約 17~22 at.%，電阻率588~ 1.33×104 μΩ-cm、硬度值29~30 GPa，與文獻比較後，發現所得為CrNxOy薄膜。接著本研究比對不同背景壓力對所鍍著薄膜的影響，發現在高背景壓力下能鍍著出與在低背景壓力品質相近的薄膜；而本研究實驗設備抽至高低背景壓力所需抽氣時間差接近10倍，因此本研究所鍍著之CrNxOy薄膜能大幅地省去抽真空的時間，達到環保與降低製程成本的目的。
It has been reported that preparation of chromium oxynitride (CrNxOy) thin films by physical vapor deposition (PVD) often requires the vacuum environment to achieve low base pressures and to avoid the influence of residual air. It usually takes much time to achieve a low base pressure and hence increases the processing cost. In the recent years, global economic recession and environment problems cause many concerns. The main purpose of this study is to prepare CrNxOy thin films at high base pressures using air as a reactive gas, which could achieve energy saving and cost reduction.
CrNxOy thin films prepared by PVD using air as a reactive gas at different base pressures (1.3×10-2 Pa、6.6×10-4 Pa) were investigated. The sputtering power was 200 W, the bias voltage was kept at -50 V, the deposition time was 20 mins, and the flow ratio of the air/Ar was varied in the range of (0~46)/100. The crystal structure of CrNxOy films was identified by X-ary diffraction. The morphology and the thickness of CrNxOy films were observed using a field-emission scanning electron microscopy. The chemical composition of the films was determined by X-ray photoelectron spectroscopy and Auger electron spectroscopy. Resistivities of the films were measured using four-point probe. The hardness of the films was measured using a nano-indenter. The residual stress of films was measured by scanning laser curvature. At high base pressure (1.3×10-2 Pa), as the flow ratio of air/Ar was controlled about (30~33)/100, the crystal structure of films were rock-salt structure. The films were columnar structure. The oxygen contant was 10~20 at%. The resistivities ranged from 588~1.33×104 μΩ-cm and the hardness ranged from 29~30 GPa. After comparing with the data reported in the literature, it has been confirmed that our study successfully prepared CrNxOy films at high base pressures. The properties of CrNxOy films prepared at high and low base pressures were similar. However, the pumping times at high and low base pressures were about ten times different. Thus, the processing time would be greatly reduced by using this process.
The results showed that CrNxOy films exhibited a rock-salt structure with oxygen concentration of 17~22 at%. The XRD results do not show any oxide phases, because oxygen atoms were not sufficient to form stable chromium oxide phases. The resistivities and hardness of the films were affected by the dissolution of oxygen atoms in the films as the films maintained a rock-salt structure.
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