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Deposition and Characteristics of TiN, TiNxOy, and N-doped TiO2 Thin Films by Sputtering Using Air as a Reactive Gas
|關鍵字:||sputtering;濺鍍法;air;TiN;TiNxOy;nitrogen-doped TiO2;空氣;氮化鈦;氮氧化鈦;氮摻雜二氧化鈦||出版社:||材料科學與工程學系所||引用:||T. Bell, and H. Dong, Advances in Surface Treatment: Research & Applications (ASTRA), T. S. Sudarshan, G. Sundararajan, G. E. Totten, and S. V .Joshi, ed. Proc. Intl. Conf., (2004). P. Ettmayer, and W. Lengauer, Nitrides: Transition Metal Solid State Chemistry, in Encyclopedia of Inorganic Chemistry, R.B. King ed. John Weily & Sons, New York, (1994) p.2498 F. Cardarelli, Materials Handbook: A Concise Desktop Reference, Spring-Verlag, Singapore, (2001) p.352, 353. H. Holleck, “Material selection for hard coatings,” J. Vac. Sci. Technol. A 4 (1986) 2661. C. Karl, W. Lengauer, D. Rafaja, and P. Ettmayer, “Critical review on the elastic properties of transition metal carbides, nitrides and carbonitrides,” J. Alloys Compd. 265 (1998) 215. E. J. Markel, and M. E. Leaphart II, Nitrides, in Encyclopedia of Chemical Technology, edited by M.H. 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Rev. Lett. 51 (1983) 1884.||摘要:||
實驗之主要變數為空氣/氬氣流量比值，範圍控制在0.05到2.00，其他製程參數則固定在工作壓力0.13 Pa、濺鍍功率400 W及基板偏壓為50V，以探討其對薄膜特性之影響。由於利用空氣做為反應性氣體，即不須在高真空，而可在較高背景壓力1.3×10-2 Pa (低真空)下操作。另有些部份會利用N2做為反應性氣體製備TiN以及空氣做為反應性氣體製備TiNxOy薄膜，此二者均在高真空下操作，以做對照。
當空氣/氬氣流量比值為0.10~0.15時，所得薄膜為岩鹽型TiN結構，N/Ti比為0.80–0.83而氧含量為9–13 at%、電阻率則為110–130 μΩ•cm、與硬度為26–27 GPa，此與文獻所報導的氮化鈦性質比對後，證實以空氣做為反應性氣體能成功製備出氮化鈦薄膜。本研究顯示在空氣/氬氣流量比值較低時，可製備出氮化鈦薄膜之原因是動力學反應主導所致。由於電漿中氧的解離能比氮的高，使氮較易解離且增加其在低流量比值時之碰撞機率。另推測氮化鈦中固溶少量的氧可以穩定氮化物的結構。
隨著空氣/氬氣流量比值增加到0.18–0.40，薄膜亦具有岩鹽型結構，然其繞射峰往高角度偏移，是為結晶之氮氧化鈦薄膜，其氧含量則增加到22–34 at%、電阻率為230–1460 μΩ•cm、硬度則為25–31 GPa。當空氣/氬氣流量比值超過0.50，結果顯示此時薄膜為非晶質結構，氧含量則增加至39–43 at%、電阻率為2×104–1×106 μΩ•cm。
當空氣/氬氣流量比值增加到1.20時，生成之薄膜為氮摻雜Ti3O5，隨著流量比達到1.40，薄膜轉變為氮摻雜Ti3O5和銳鈦鑛相TiO2混合相。而在流量比值增加到1.80時可得到氮摻雜銳鈦鑛相TiO2。XPS結果顯示氮摻雜銳鈦鑛TiO2氧含量可達7.5 at%。氮摻雜銳鈦鑛TiO2能隙為3.05-3.11 eV，且其能隙隨氮含量增加呈線性下降趨勢。利用可見光可降解亞甲基藍染劑之實驗，顯示氮摻雜銳鈦鑛二氧化鈦具有極佳可見光光觸媒效應。
本研究單純控制不同空氣/氬氣流量比，不僅可製備氮化鈦、氮氧化鈦及氮摻雜二氧化鈦單層薄膜，亦可製備Ti/TiN/TiNxOy/N-doped TiO2 等之多層膜。此製程研究方法簡便且可大幅縮短製程時間，更可應用至其他類似氮化物、氮氧化物與氮摻雜氧化物之薄膜系統，具有極廣泛的工業用途。
This study focuses on the preparation and characterization of TiN, TiNxOy, and N-doped TiO2 thin films by reactive sputtering using air as a reactive gas. The films exhibiting many superior physical and chemical properties are of technologically important materials and conventionally prepared by reactive sputtering using nitrogen and/or oxygen as reactive gases. Replacing nitrogen and/or oxygen with air as a reactive gas allows the process to be conducted at high base pressures (low vacuum), which can then reduce drastically the processing time and lead to many industrial applications.
The prime deposition variable was simply the air/Ar flow ratio that was varied in a wide range of 0.05-2.00. The deposition parameters of the working pressure (= 0.13 Pa), power (= 400 W), and substrate bias (= 50 V) were fixed throughout the study. Since air was used as a reactive gas, high vacuum was not needed and the base pressure of 1.3×10-2 Pa (low vacuum) was conducted. For comparison in some cases, N2 was also used as a reactive gas for making TiN films at a low base pressure of 6.6×10-4 Pa (high vacuum), whereas TiNxOy films were also prepared by using air as a reactive gas in such a base pressure.
As the air/Ar flow ratio reached 0.10-0.15, the films revealed the characteristic rock-salt structured TiN. The N/Ti of the films was 0.80-0.83 with 9-13 at% of oxygen. The determined resistivities and hardnesses of the films were in the range of 110-130 μΩ∙cm and 26-27 GPa, respectively. All obtained data fulfill the characteristics of TiN films. Kinetic formation apparently prevails over thermodynamic predictions at low air/Ar ratios. In such plasma, the dissociation energy of oxygen is much larger than that of nitrogen, which enhances the impingement rate of nitrogen. The dissolution of oxygen in the TiN films seems also to stabilize the nitride structure.
When the air/Ar ratio was in the range of 0.18-0.40, the films had the rock-salt structure with the diffraction peaks shifting to higher angles, characterized as crystalline TiNxOy. As the ratio exceeded 0.50, the films were amorphous. The oxygen content in the TiNxOy films increased from 22-34 at% (crystalline) to 39-43 at% (amorphous). The resistivity was about 230-1460 μΩ•cm in the crystalline regime and increased rapidly up to 2×104-1×106 μΩ•cm as the films were amorphous. The hardness of the crystalline TiNxOy films was in the range of 25-31 GPa.
As the air/Ar flow ratio reached 1.20, the obtained films were N-doped Ti3O5 and transformed into N-doped Ti3O5 with N-doped TiO2 mixed phases at the air/Ar ratios of 1.40-1.60. N-doped anatase TiO2 films obtained at the air/Ar ratios of 1.80-2.00 could incorporate up to about 7.5 at% of substitutional nitrogen. The measured optical band gaps of the N-doped anatase TiO2 films varied from 3.05 to 3.11 eV. The band gap decreased almost linearly with the nitrogen concentration. N-doped TiO2 films exhibited superior visible-photocatalytic properties from the degradation of Methylene blue test.
The band structures of the anatase TiO2 with oxygen vacancies and/or N dopants were calculated using the CASTEP program. The substitutional dopant (NO) was more photocatalytic-effective than the interstitial dopant NI(c), while the band gap increased with increasing the oxygen vacancies. The calculations for the anatase TiO2 with a vacancy and various N dopants concentration reveal that the band gap decreased with the concentration of N dopants, which verifies our above experimental results.
Tailoring simply the air/Ar flow ratios in sputtering can yield not only single layers but multilayers consisting of TiN, TiNxOy, and N-doped TiO2 thin films. This green technique may be extended to make other similar nitride, oxynitride, and nitrogen-doped oxide thin film systems, which has great industrial applications.
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