射频磁控溅射法制备类金刚石薄膜的研究
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摘要
类金刚石碳(DLC)膜，具有高硬度、高耐磨性、低摩擦系数、高热导率、高红外透过率、高化学稳定性等一系列与金刚石膜相似的优异性能。与金刚石膜相比，其具有沉积温度低、沉积面积大、膜面平整光滑、成本低等优点，是一种优良的红外增透保护材料。本文研究了射频磁控溅射法制备无氢和含氢DLC膜的主要工艺参数对薄膜沉积速率的影响，并对两种不同工艺下制备的薄膜性能进行了分析比较。主要研究结果如下：
利用OPFCAD软件在Si衬底和ZnS衬底上设计了单面、双面镀单层DLC膜的增透膜系，并对所设计的膜系进行了结构偏差分析。膜系设计结果表明，Si衬底上镀DLC膜后可以很好的实现3～5μm波段的红外增透。DLC／GaP(厚层)增透保护膜系在长波红外波段对ZnS衬底能起到较好的增透作用。
在射频磁控溅射设备上进行了制备无氢和含氢DLC膜的工艺试验，系统地研究了射频功率、溅射气压、气体流量以及衬底温度对薄膜沉积速率的影响规律。结果表明，对于无氢DLC膜，沉积速率随射频功率的增大而增大，随溅射气压的增大先增大后减小，衬底温度对沉积速率的影响不大。而在制备含氢DLC膜过程中发现，沉积速率随射频功率、溅射气压、CH_4气体流量的增大而增大，随着衬底温度的升高呈现先增大后减小的趋势。
对所制备的DLC膜进行了AFM、XRD、Raman分析。结果表明，随着功率的增大，两种薄膜的粗糙度均有所增大，含氢DLC膜的粗糙度整体要比无氢DLC膜的低。DLC膜由sp~2键镶嵌在sp~3键基体中构成。所制备的两种DLC膜均呈非晶态。
使用FITR光谱仪分析了Si衬底上镀DLC膜的红外透过性能。在3～5μm波段，两种膜都有着很好的增透效果，峰值透过率达97％以上。在ZnS衬底上成功制备出DLC／GaP(厚层)膜系，在长波红外波段对ZnS具有较好的红外增透效果，峰值处可增透10％以上。
Diamond-like carbon (DLC) film is an amorphous carbon film that exhibits a series of excellent properties such as high hardness, good chemical inertness, high thermal conductivity, good transmittance in infrared and low wear coefficient. Compared with diamond film, DLC film has lower deposition temperature, larger deposition scale and smoother surface. It can be used as a new IR antirefiective and protective material. Researches of this paper concentrate mostly on the preparation, structure and infrared transmission of sputtered α-C films and sputtered α-C: H films. The main research works and results are as follows:
Anti-reflection film systems containing DLC are designed on Si substrates and ZnS substrates, and deviation of the film system's structure is analyzed. The designed results show that the film systems own good transmission on Si and ZnS substrate.
Sputtered α-C films and sputtered α-C: H films have been prepared using RF magnetron sputtering apparatus on Si (111) substrates in order to research the influences of the main experiment parameters such as RF power, gas flow, vacuum gas pressure and substrate temperature on the film deposition rate respectively. The investigations show that the deposition rate increases with the increasing of sputtering power, and initially increases and then decreases with the increasing of sputtering pressure, but is insensitive to the substrate temperature in the preparation of the sputtered α-C films. The investigation shows that the deposition rate increases with the increasing of sputtering power, CH4 gas flow and vacuum gas pressure, but initially increases and then decreases with the increasing of substrate temperature in the preparation of the sputtered α-C: H films.
AFM analyses show that the RMS rough increases with the increasing of sputtering power. The surface of the sputtered α-C: H film is smoother than the sputtered α-C film. Raman analyses show that sputtered α-C films and sputtered α-C: H films both contain sp~3 and sp~2 bonds. XRD results show that deposited DLC films are amorphous.
FTIR transmission spectrum results confirm the average transmittance at a wavelength of 3～5μm of Si coated with one layer of sputtered α-C: H films on two
利用OPFCAD软件在Si衬底和ZnS衬底上设计了单面、双面镀单层DLC膜的增透膜系，并对所设计的膜系进行了结构偏差分析。膜系设计结果表明，Si衬底上镀DLC膜后可以很好的实现3～5μm波段的红外增透。DLC／GaP(厚层)增透保护膜系在长波红外波段对ZnS衬底能起到较好的增透作用。
在射频磁控溅射设备上进行了制备无氢和含氢DLC膜的工艺试验，系统地研究了射频功率、溅射气压、气体流量以及衬底温度对薄膜沉积速率的影响规律。结果表明，对于无氢DLC膜，沉积速率随射频功率的增大而增大，随溅射气压的增大先增大后减小，衬底温度对沉积速率的影响不大。而在制备含氢DLC膜过程中发现，沉积速率随射频功率、溅射气压、CH_4气体流量的增大而增大，随着衬底温度的升高呈现先增大后减小的趋势。
对所制备的DLC膜进行了AFM、XRD、Raman分析。结果表明，随着功率的增大，两种薄膜的粗糙度均有所增大，含氢DLC膜的粗糙度整体要比无氢DLC膜的低。DLC膜由sp~2键镶嵌在sp~3键基体中构成。所制备的两种DLC膜均呈非晶态。
使用FITR光谱仪分析了Si衬底上镀DLC膜的红外透过性能。在3～5μm波段，两种膜都有着很好的增透效果，峰值透过率达97％以上。在ZnS衬底上成功制备出DLC／GaP(厚层)膜系，在长波红外波段对ZnS具有较好的红外增透效果，峰值处可增透10％以上。
Diamond-like carbon (DLC) film is an amorphous carbon film that exhibits a series of excellent properties such as high hardness, good chemical inertness, high thermal conductivity, good transmittance in infrared and low wear coefficient. Compared with diamond film, DLC film has lower deposition temperature, larger deposition scale and smoother surface. It can be used as a new IR antirefiective and protective material. Researches of this paper concentrate mostly on the preparation, structure and infrared transmission of sputtered α-C films and sputtered α-C: H films. The main research works and results are as follows:
Anti-reflection film systems containing DLC are designed on Si substrates and ZnS substrates, and deviation of the film system's structure is analyzed. The designed results show that the film systems own good transmission on Si and ZnS substrate.
Sputtered α-C films and sputtered α-C: H films have been prepared using RF magnetron sputtering apparatus on Si (111) substrates in order to research the influences of the main experiment parameters such as RF power, gas flow, vacuum gas pressure and substrate temperature on the film deposition rate respectively. The investigations show that the deposition rate increases with the increasing of sputtering power, and initially increases and then decreases with the increasing of sputtering pressure, but is insensitive to the substrate temperature in the preparation of the sputtered α-C films. The investigation shows that the deposition rate increases with the increasing of sputtering power, CH4 gas flow and vacuum gas pressure, but initially increases and then decreases with the increasing of substrate temperature in the preparation of the sputtered α-C: H films.
AFM analyses show that the RMS rough increases with the increasing of sputtering power. The surface of the sputtered α-C: H film is smoother than the sputtered α-C film. Raman analyses show that sputtered α-C films and sputtered α-C: H films both contain sp~3 and sp~2 bonds. XRD results show that deposited DLC films are amorphous.
FTIR transmission spectrum results confirm the average transmittance at a wavelength of 3～5μm of Si coated with one layer of sputtered α-C: H films on two
引文
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10. Dilllon R O, Woollam J A, Katkanant V. Use of Raman scattering to investigate disorder and crystalline domination in as-deposited and annealed carbon films. Phys Rev, 1984, B29:3482
11. Tay B K, Shi X, Tan H S, et al. Raman studies of tetrahedral amorphous carbon films deposited by filtered cathode vacuum arc. Surf Coat Technol, 1998,105:155
12. Musil J, Vlcek J. A perspective of magnetron sputtering in surface engineering. Surf Coat Technol, 1999,(112): 162
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18. B Discheler, E Bayer. J Appl Phys.1990, 68:1237
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36. D.R. Gibson and E.M. Waddell. Advances in ultra durable Phosphide-based broadband anti-reflective coatings for sand and rain erosion protection of infrared windows and domes. Proc. SPIE, 1994, 2286:335
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2. Brierley C J, Costello M C, Hudson M D, et al. Diamond Coating for Large Area IR Windows. Proc. SPIE, 1994, 2286:307～315
3. Robertson J. Diamond-like amorphous carbon. Materials Science and Engineering R 37(2002)129～281
4. Mennella V, Monaca G, Colangeli L, et al. Raman spectra of carbon-based materials excited at 1064nm. Carbon, 1995,33:115
5. Scheibe H J, Drescher D, Alers P. Raman characterization of amorphous carbon films [J]. Fresenius J Anal Chem, 1995, 353:695
6. Robertson J. Properties of diamond-like carbon. Surf Coat Technol, 1992, 50:185
7. Capano M A, Mcdevitt N T, Singh D K, et al. Characterization of amorphous carbon thin films. J Vac Sci Technol, 1996, A14:431
8. Knight D S, White W B. Characterization of diamond films by Raman spectroscopy. J Mater Res, 1989, 4:385
9. Schwan J, Ulrich S, Bathori V, et al. Raman spectroscopy on amorphous carbon films. J Appl Phys, 1996,80:440
10. Dilllon R O, Woollam J A, Katkanant V. Use of Raman scattering to investigate disorder and crystalline domination in as-deposited and annealed carbon films. Phys Rev, 1984, B29:3482
11. Tay B K, Shi X, Tan H S, et al. Raman studies of tetrahedral amorphous carbon films deposited by filtered cathode vacuum arc. Surf Coat Technol, 1998,105:155
12. Musil J, Vlcek J. A perspective of magnetron sputtering in surface engineering. Surf Coat Technol, 1999,(112): 162
13．郑伟涛．薄膜技术与薄膜材料．北京：化学工业出版社，2004，第六章：262
14．茅东升．无氢非晶金刚石薄膜的制备及其电子场发射性能研究．中国科学院上海冶金研究所博士论文．2000：39
15. Lifshitz Y, Kasi S R,et al.Mater Sci Forum. 1989,52～53:237
16. Fujimori S, Kasai T and Inamura T. Carbon film formation by laser evaporation and ion beam sputtering. Thin Solid Films. 1982,Vol.92:71
17. Ishii A, Amadafsu S, Minomos, J Vac Sci Technol, 1994:12(4):1068
18. B Discheler, E Bayer. J Appl Phys.1990, 68:1237
19．郑伟涛．薄膜技术与薄膜材料．北京：化学工业出版社，2004，第二章：30
20. Tsai Hsiao-chu, Bogy D B. Characterization of diamond-like carbon films and their application as overcoats on thin-films media for magnetic recording. J Vac Sci Technol A, 1987, 5(8):3287-3312
21．贺小明．离子束辅助沉积类金刚石碳膜研究，清华大学博士学位论文，1994
22. Michler T, et al. Surf Coat Technol.1987, A5(6):3287
23. Pethica J B, et al. In ion implantation into metals. Pergamon Oxford, 1982:147
24. Sushil Kumar, Dsarangi, et al. Diamond-like carbon films with extremely low stress. Thin Solid Films 346(1999)
25．Luo G N，et al．96中国材料研讨会论文集．1-3分册：439
26. Voevodiu A A, et al. Wear resistant composite coatings deposited by electron enhanced closed field unbalanced magnetron sputtering. Surf Coat Technol. 1995(73):185
27. Kazukisa Mryoshi, et al. Sci Technol Aerrsp Rep. 1992,30(14):23192
28．张贵峰等．类金刚石薄膜作为MgF_2红外增透和保护膜的研究．光电子技术，1996，16(2)：113～118
29．林锡刚，雍志华，刘玮等．低能离子束沉积类金刚石膜的结构及性能研究．功能材料，1997，28(1)：84
30．姜杰．高性能的类金刚石的红外光学薄膜．红外技术，1996，18(4)：15～20
31. Hsiao-chu Tsai, et al. J. Vac Sci Technol. 1987, A5(6):3287
32. Chuang F Y, et al. Int Vac Microelectron Conf Tech Dig. 1997(10):541
33．宋建全．ZnS头罩增透保护膜系的设计、制备及计算机模拟．西北工业大学博士学位论文，2001：2
34. E M Waddell, D R Gibson, J Meredith. Sand impact testing of durable coatings on FLIR ZnS relevant to the lantern E-O system window. SPIE, 1994, 2286:364-375
35. E M Waddell, D R Gibson, M Wilson. Broadband IR transparent rain and sand erosion protective coating for the F14 aircraft infra-red search & Germanium dome. SPIE, 1994, 2286:376-385
36. D.R. Gibson and E.M. Waddell. Advances in ultra durable Phosphide-based broadband anti-reflective coatings for sand and rain erosion protection of infrared windows and domes. Proc. SPIE, 1994, 2286:335
37．宋健民．超硬材料．台湾泉华科技图书股份有限公司，2000，第8章：17
38．戴达煌，周克菘等．金刚石薄膜沉积制备工艺与应用．北京．冶金工业出版社，2001，
39．李忠奇，姜杰．类金刚石薄膜的制备，特性及应用．光学学报，1990．10(11)：1016
40．张贵锋，耿东生，郑修麟；．金刚石薄膜的红外光学性能．激光与红外，1997．27(1)：51
41. Craig S, Harding G I. Structure optical properties and decomposition kinetics of sputtered hydrogenated carbon. Thin Solid Films, 1982, 97:354-361
42. Popescu B, et al. Hydrogen incorporation and its structural effect on a-C: H films deposited by magnetron sputtering. Journal of Non-Crystalline Solids, 2000, 266-269:803-807
43．林永昌，卢维强．光学薄膜原理．国防工业出版社，1990
44．严瑛白．应用物理光学．机械工业出版社，1990：71．
45．Macleod H A光学薄膜技术．周九林，尹树百(译)．国防工业出版社，1974：23
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