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標題: Characteristics and processing windows of Cr-N-O thin films prepared by DC magnetron sputtering using air as a reactive gas
作者: Tsai, Cheng-Lin
關鍵字: sputtering;濺鍍法;air;Cr-N-O thin films;空氣;Cr-N-O 薄膜
出版社: 材料科學與工程學系所
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本研究之目的是利用空氣做為反應性氣體以取代高成本的氮氣或氧氣,並且在高背景壓力(低真空度)下製備出不同類型的Cr-N-O薄膜,由於大幅減少真空系統抽氣所耗費的時間,在工業應用上可達到降低製程成本及節能之綠色製程的目標。製程主要是以直流磁控濺鍍法,在背景壓力1.3×10-2 Pa(低真空)、工作壓力0.21–0.36 Pa、空氣/氬氣(air/Ar)流量比0–2.00、濺鍍功率100和400 W、基板偏壓-50 V、時間20分鐘之條件製備Cr-N-O薄膜。探討不同之air/Ar通入流量比及濺鍍功率對薄膜結晶相化學組成、電性、硬度及光學能隙之影響。
當濺鍍功率400 W,air/Ar流量比值為0–0.05時,沉積所得薄膜經X光繞射(XRD)分析具有體心立方Cr相結構,四點探針量測電阻率為31–75 μΩ–cm,所得之薄膜為Cr。而air/Ar流量比值在0.10–0.35範圍,電阻率為102–260 μΩ–cm,藉由奈米壓痕儀量測所得之硬度約為19.2–21.2 GPa,此外,XRD結果在2θ約42°–46°有一寬繞射峰表示生成之薄膜有混合相存在,綜合分析後得知此薄膜由Cr/Cr2N/CrN/CrNxOy組成。當air/Ar流量比到達0.40–0.50,所得薄膜為岩鹽型CrN結構,X光光電能譜儀(XPS)分析結果顯示N/Cr成份比為0.38–0.46而O含量為19.7–30.8 at%,薄膜電阻率為326–4.2×10+5 μΩ–cm及硬度為17.0–24.0 GPa,皆符合文獻中CrNxOy之性質,因此薄膜為結晶CrNxOy。接著提高air/Ar流量比至0.55–0.60,生成之薄膜具有非晶相結構,薄膜硬度為20.9–24.0 GPa,N/Cr比變為0.21–0.23但O含量高達42.5–45.1 at%,造成電阻率超出四點探針可量測範圍,顯示此時薄膜已轉變為非晶CrNxOy結構。通入air/Ar流量比為0.80–2.00範圍,薄膜結構為非晶相,而由紫外/可見光光譜(UV-Vis)分析所得光學能隙為3.10–3.31 eV,由於其成分中N/Cr比降至0.05–0.07而O/Cr比達到1.20–1.27,表示薄膜已轉變為氮摻雜之CrOx。
以濺鍍功率100 W僅通入Ar時,鍍著後的薄膜結晶相為體心立方Cr結構,電阻率為161 μΩ–cm,所得之薄膜為Cr。在air/Ar流量比為0.02–0.10,薄膜由XRD分析顯示在2θ約42°–46°也存在寬繞射峰,其電阻率180–554 μΩ–cm,生成薄膜具有Cr/Cr2N/CrN/CrNxOy混合結晶相。增加air/Ar流量比至0.15–2.00時,生成非晶相薄膜的光學能隙為2.98–3.29 eV,此時為氮摻雜之CrOx薄膜。

The objective of this study is to prepare different Cr-N-O thin films by using air as a reactive gas instead of conventional used nitrogen and oxygen gas. The process was conducted at high base pressures (low vacuum), which could substantially reduce the pumping time to achieve the aims of lowering manufacturing cost and saving energy in industrial applications. The deposition was conducted by DC magnetron sputtering at air/Ar flow ratios varying from 0 to 2.00; two sputtering powers of 100 W and 400 W were selected; the base pressure was 1.3×10-2 Pa; the working pressure was varied in the range of 0.21-0.36 Pa; the bias voltage was kept at -50 V; the sputtering time was fixed at 20 minutes. The crystal structures, chemical compositions, resistivity, hardness, and optical band gap of the deposited films at different air/Ar flow ratios and sputtering power were investigated.
As the sputtering power was 400 W and air/Ar ratio was 0-0.05, the films were identified to be the body-centered cubic Cr structure by X-ray diffraction(XRD). The resistivities of the films measured by a four probe system were about 31-75 μΩ-cm. The obtained films were Cr. When the air/Ar ratios were in the range of 0.10-0.35, the resistivities of the films were between 102 and 260 μΩ-cm, and the hardnesses obtained by using a nanoindentor were 19.2-21.2 GPa. Furthermore, the films possessed mixed phase structures, which were revealed by a broad diffraction peak around 42°-46°(2θ). Based on above analyses, the films consisted of Cr/Cr2N/CrN/CrNxOy. As the air/Ar ratio rose to 0.40-0.50, the deposited films had a CrN rock-salt structure. X-ray photoelectron spectroscopy(XPS) analysis indicated that the N/Cr ratios of the films were 0.38-0.46 with 19.7-30.8 at% of oxygen. The resistivities and hardnesses of the films were 326-4.2×10+5 μΩ-cm and 17.0-24.0 GPa, respectively. The films possessed crystalline CrNxOy. When the air/Ar ratio increased to 0.55-0.60, the obtained films were amorphous. The hardnesses of the films were about 20.9-24.0 GPa. The N/Cr ratio of the films decreased to 0.21-0.23 while the oxygen of the films increased up to 42.5-45.1 at%, thus the measured resistivitiy was out of the scale. The results indicated that the CrNxOy films could transform from crystalline into amorphous. Moreover, the structure of the films changed to N-doped CrOx phase as the air/Ar ratio reached 0.80-2.00. Because the N/Cr ratios of the films declined 0.05-0.07 and the O/Cr ratios of the films were up to 1.20-1.27. The optical band gaps of the films that calculated from UV-Vis spectra were in the range of 3.10-3.31 eV.
When the sputtering power of 100 W was applied and only Ar was used, the deposited films also exhibited a body-centered cubic structure. The resistivity of the films was 161 μΩ-cm. The obtained films were Cr. As the air/Ar ratio reached 0.02-0.10, the resistivities of the films were in the range of 180-554 μΩ-cm. The broad peak of each specimen utilizing XRD was in the neighborhood of 42°-46°(2θ). According to the results, the films exhibited mixed Cr/Cr2N/CrN/CrNxOy phases. Moreover, amorphous N-doped CrOx films could be obtained at the air/Ar ratios of 0.15-2.00, and the optical band gaps of the films were varied from 2.98-3.29 eV.
The process windows of the Cr-N-O thin films at various air/Ar flow ratios as well as the sputtering powers were investigated. Therefore, the structures of Cr-N-O thin films at different air/Ar ratios could be successfully identified. Moreover, the formation of the films predominated by two mechanisms: kinetics and thermodynamics, which depend on the air/Ar flow ratios. Results indicated that the film deposition was predominated by the kinetics mechanism at lower air/Ar flow ratios, which resulted in the different structures of Cr, mixed Cr/Cr2N/CrN/CrNxOy, crystalline and amorphous CrNxOy observed in the films. On the other hand, the films became N-doped CrOx as the air/Ar flow ratio was relatively high, which is due to the thermodynamics governed formation.
其他識別: U0005-2208201102514400
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