塑料材质上装饰性薄膜的设计和制备
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摘要
装饰性薄膜应用领域非常广泛。其一般设计方法是滤光膜系设计法，这种方法不仅繁琐，而且所需的膜层数多，实际生产中需要很高的镀膜工艺技术。本文重点讨论一种改进的塑料基材装饰性薄膜设计法，并解决了薄膜制备过程中遇到的一些关键性问题。以薄膜干涉理论为基础，导出了薄膜干涉产生的颜色与膜厚间关系，并据此设计出比较简单的膜系结构，降低了对镀膜工艺的要求；在磁控溅射制备单质金属(如Al、Ni、Cr)装饰膜以及彩色装饰膜过程中，通过对薄膜膜厚均匀性影响因素的分析，调整工艺参数，解决了镀制高透薄膜时，由于膜厚均匀性而引起的生产率下降问题；从光学塑料的特性出发，通过薄膜附着力理论分析，改变工艺参数，解决了Al膜与塑料基材附着力差的问题；通过薄膜膜系应力理论分析，提出在彩色装饰膜系中的金属膜表面镀制一层致密介质薄膜，结果不仅保护了金属膜，减少了潮气影响，还可以使整个膜系所受的应力减少，有效改善了薄膜附着力。
Decorative coatings have found wide application in practice. Usually these coatings are designed with filter method which is very complicated, and the structures of designed stacks are complex and prove hard for production. This paper mainly focuses on a new design method for decorative coatings deposited on plastic substrate, and solves some key technical problems encountered in the fabrication of the coatings. Based on the theory of thin film interference, the relationship between the reflective color and film thickness is deduced and corresponding multilayer is designed. The newly designed stack is much simple and can be easily made in mass-production scale. Metallic decorative film (Al, Ni and Cr) and colorful decorative film are prepared by magnetron sputtering technique. Based on the analysis of the factors that affect thickness uniformity, some technical parameters related to the film production are adjusted and uniform film is acquired, thus significantly raises the productivity of the deposition of metallic film with high transmissivity on plastic substrates. By analysis of the characteristics of the plastic substrate and utilization of film adhesion theory, the adhesion between Al and substrate is greatly improved in the production of magnetron sputtering metallic Al film. Since metallic film is the outmost layer of the colorful decorative multilayer, compact dielectric film is over coated on its surface to protect the metallic film from the erosion of moister. The addition of the dielectric film can also reduce the stress of the stack, therefore improve the adhesion of the film.
Decorative coatings have found wide application in practice. Usually these coatings are designed with filter method which is very complicated, and the structures of designed stacks are complex and prove hard for production. This paper mainly focuses on a new design method for decorative coatings deposited on plastic substrate, and solves some key technical problems encountered in the fabrication of the coatings. Based on the theory of thin film interference, the relationship between the reflective color and film thickness is deduced and corresponding multilayer is designed. The newly designed stack is much simple and can be easily made in mass-production scale. Metallic decorative film (Al, Ni and Cr) and colorful decorative film are prepared by magnetron sputtering technique. Based on the analysis of the factors that affect thickness uniformity, some technical parameters related to the film production are adjusted and uniform film is acquired, thus significantly raises the productivity of the deposition of metallic film with high transmissivity on plastic substrates. By analysis of the characteristics of the plastic substrate and utilization of film adhesion theory, the adhesion between Al and substrate is greatly improved in the production of magnetron sputtering metallic Al film. Since metallic film is the outmost layer of the colorful decorative multilayer, compact dielectric film is over coated on its surface to protect the metallic film from the erosion of moister. The addition of the dielectric film can also reduce the stress of the stack, therefore improve the adhesion of the film.
引文
[1] 陈季芝，王浩．反应气体组成对TiN颜色得影响[J]．薄膜科学与技术，1989，2 (2)：12．
[2] 张纯．TiN镀层表面颜色研究．真空科学与技术[J]，1995，15 (6)：391．
[3] Karlsson B. Optical constants and spectral selectiving of titanium carbonitrides. Thin Solid Films, 1982, 87: 181.
[4] Mumtaz A, Class W H. Color of TiN prepared by reactive the magnetron sputtering. J. Vac. Sci. Technol., 1982, 20(3): 345.
[5] Geory R, Uwe B, Hermann A J. Decorative optical coatings. Thin Solid Films, 1994, 253: 33.
[6] Perry A J, Georyson M, Ribbing C G. The reflectance and color of TiN. J. Vac. Sci. Technol. A, 1986, 4(6): 2674.
[7] Rivory J. Optical properties of substoichiometric TiN_x. Thin Solid Films, 1981, 78: 161.
[8] Uwe B, Ceory R, Klass W. Decorative hard coatings: advances in optical characterization techniques. Thin Solid Films, 1993, 236: 184.
[9] 孙亚军 王先玉 任兆杏．装饰膜层光学性能得理论分析[J]．真空与低温，1996，12：217～222．
[10] Sproul W D. The effect of N_2 partial pressure, deposition rate and sibstrate bias potential on the hardness and texture of reactively sputtered TiN coatings. Surface and coatings Techology, 1989. 39: 355
[11] Komiya S, Tsuruoka K. Japan J. Appl. Suppl., 1974, 2: 415.
[12] 唐晋发，顾培夫．现代光学薄膜技术[M]．杭州：浙江大学出版社，2006．
[13] 常天海．反射及透射红色薄膜的膜系设计[J]．真空与低温，2004，10：108～111．
[14] 邱沛和．望远镜反红膜[J]．现代机械，1999，1：80～81．
[15] 常天海．遗传算法在窄带滤光片膜系设计中的应用[J]．真空与低温，2002，8(4)：225～229．
[16] 黄祥成，杨益民，杨华，张万虎．绿色薄膜的膜系结构[J]．应用光学，1999，20(1)：36～40．
[17] 李颜霞．塑料真空镀膜[M] 北京：化学工业出版社，1990．
[18] 白秀琴，李键，严新军，赵春华．真空镀膜技术在塑料表面金属化上的作用[J]．武汉理工大学学报，2005，6：947～950．
[19] 合肥工业大学真空教研室，真空镀膜技术与设备[M]．2003．
[20] Hans Joachim Glaser 著，德国冯·阿灯纳真空技术有限公司组织翻译．大面积玻璃镀膜[M]．上海交通大学出版社，2004．
[21] 唐伟忠．薄膜材料制备原理、技术及应用[M]．冶金工业出版社，2005．
[22] 邵淑英．薄膜应力的产生机理与控制技术研究[J]．博士毕业论文，2005．
[23] Angus Macleod．Optical Comings from Design through Manufacture[M]．浙江大学信息学院光学薄膜研究中心，译．2003．
[24] 郭永康．光学[M]．北京：高等教育出版社，2005
[25] 钟迪生．真空镀膜—光学材料的选择与应用[M]．沈阳：辽宁大学出版社，2001．
[26] 林永昌，卢维强．光学薄膜原理[M]．北京：国防工业出版社，1990．
[27] 秦跃利，高能武，吴云海．改进工艺提高薄膜附着力[J]．电子元件与材料，2000，1：26～27．
[28] 潘永强，卢进军 光学塑料真空镀膜附着力机理与工艺研究[J]．应用光学，2003，24(3)：32～34．
[29] 孙亦宁．中间层对薄膜附着力强度的改进[J]．真空于低温。1999，6：70～76．
[30] Mattox D M. Surface Effects on the Growth Adhesion and Propertics of Reactively Deposited Hard Coatings. Surface and Coatings Technology. 1996 81. 8～16.
[31] 谢致微，蒙继龙，王国庆．物理气相沉积薄膜的界面与附着力[J]．2001，5：203～208．
[32] 腾林，杨邦朝，崔红玲，杜晓松．金属薄膜附着性的改进[J]．电子元件与材料，2003，6：41～44．
[33] 赵峰．影响磁控阴极溅射法镀膜玻璃质量的原因及解决办法[J]．玻璃，1994，3：36～45．
[34] 王怡德．磁控溅射技术[M]．北京：北京中方盖德真空技术有限公司．
[35] 龚建华．镀膜玻璃膜层均匀性探讨[J]．真空，1996，2：20～24．
[36] 赵峰，商文库．镀膜玻璃的膜系特性及生产工艺控制[J]．玻璃，1996，6：37～42．
[37] 龚建华，张永胜，柳俊文．大面积玻璃基片磁控溅射真空镀膜简介(二)．真空，2006，3：1～4
[38] 杨友财．大面积玻璃基片磁控溅射镀膜膜层性质和特性的研究．硕士毕业论文，2007．
[39] 徐成海．真空工程技术[M]．北京：化学工业出版社，2006．
[40] 袁超．多层薄膜材料界面能的测定与分析[J]．硕士毕业论文，2003．
[41] L．B．Freund，S．Suresh著，卢磊译．薄膜材料—应力、缺陷的形成和表面演化[M]．北京：科学出版社，2007．
[42] Abermann. R, Measurements of the intrinsic stress in thin metal films, vacuum, 1990(41): 1279～1282.
[43] S Tamulevicius,Stress and strain in the vacuum deposited thin films,vacuum,Vacuum,1998,V5,No2,pl27～139.
[44] F.Spaepen,Interfaces and stresses in thin films,Acta mater 2000,V48,p31-42.
[45] D.W.Hoffman,J.A. Thornton,The compressive stress transition in Al,V,Zr,Nb and W metal films sputtered at low working pressures,Thin Solid Films. 1977,Vol .45,No,2,387～396.
[46] D.W.Hoffman,J.A.Thornton, Internal stresses in sputtered chromium, Thin Solid Films.l977,Vol.40,355～363.
[47]J.A.Thornton,D.W.Hoffman. Internal stresses in titanium,nickel,molybdenum,and tantalum films deposited by cylindrical magnetron sputtering, J.Vac. Sci. Technol,1977,Vol.14,No.1,164～168.
[48] J.A.Thornton, Magnetron sputtering: basic physics and application to cylindrical magnetrons,J.Vac. Sci. Technol,1978,Vol.14,No.2,171～177.
[49] D.W.Hoffman,J.A. Thornton, Effects of substrate orientation and rotation on internal stresses in sputteredmetal films, J.Vac. Sci.Technol, 1979,Vol.16,No.2,134.
[50] D.W.Hoffman,M.R. Gaerttner,Modification of evaporated chronmium by concurrent ion bombardment, J.Vac. Sci. Technol,1980,Vol.17,No.1,425～428.
[51] Wu C T, Kampwirth R T, Hafstrom J W, High-rate magnetron sputtering of high T_cNb_3S_n films, J.Vac. Sci. Technol,1977,Vol.14,No.1,134～137.
[52] H.Windischmann,Intrinsic stress in sputtered thin films, J.Vac. Sci.Technol,1991,A9(4),2431～2436.
[53] A.Entenberg,V. Lindbcrg, K.Fletcher, Stress measurement in sputtered copper films on flexible polyimide substrates, J.Vac. Sci. Technol, 1987,A5 , No.6,3373～3377.
[2] 张纯．TiN镀层表面颜色研究．真空科学与技术[J]，1995，15 (6)：391．
[3] Karlsson B. Optical constants and spectral selectiving of titanium carbonitrides. Thin Solid Films, 1982, 87: 181.
[4] Mumtaz A, Class W H. Color of TiN prepared by reactive the magnetron sputtering. J. Vac. Sci. Technol., 1982, 20(3): 345.
[5] Geory R, Uwe B, Hermann A J. Decorative optical coatings. Thin Solid Films, 1994, 253: 33.
[6] Perry A J, Georyson M, Ribbing C G. The reflectance and color of TiN. J. Vac. Sci. Technol. A, 1986, 4(6): 2674.
[7] Rivory J. Optical properties of substoichiometric TiN_x. Thin Solid Films, 1981, 78: 161.
[8] Uwe B, Ceory R, Klass W. Decorative hard coatings: advances in optical characterization techniques. Thin Solid Films, 1993, 236: 184.
[9] 孙亚军 王先玉 任兆杏．装饰膜层光学性能得理论分析[J]．真空与低温，1996，12：217～222．
[10] Sproul W D. The effect of N_2 partial pressure, deposition rate and sibstrate bias potential on the hardness and texture of reactively sputtered TiN coatings. Surface and coatings Techology, 1989. 39: 355
[11] Komiya S, Tsuruoka K. Japan J. Appl. Suppl., 1974, 2: 415.
[12] 唐晋发，顾培夫．现代光学薄膜技术[M]．杭州：浙江大学出版社，2006．
[13] 常天海．反射及透射红色薄膜的膜系设计[J]．真空与低温，2004，10：108～111．
[14] 邱沛和．望远镜反红膜[J]．现代机械，1999，1：80～81．
[15] 常天海．遗传算法在窄带滤光片膜系设计中的应用[J]．真空与低温，2002，8(4)：225～229．
[16] 黄祥成，杨益民，杨华，张万虎．绿色薄膜的膜系结构[J]．应用光学，1999，20(1)：36～40．
[17] 李颜霞．塑料真空镀膜[M] 北京：化学工业出版社，1990．
[18] 白秀琴，李键，严新军，赵春华．真空镀膜技术在塑料表面金属化上的作用[J]．武汉理工大学学报，2005，6：947～950．
[19] 合肥工业大学真空教研室，真空镀膜技术与设备[M]．2003．
[20] Hans Joachim Glaser 著，德国冯·阿灯纳真空技术有限公司组织翻译．大面积玻璃镀膜[M]．上海交通大学出版社，2004．
[21] 唐伟忠．薄膜材料制备原理、技术及应用[M]．冶金工业出版社，2005．
[22] 邵淑英．薄膜应力的产生机理与控制技术研究[J]．博士毕业论文，2005．
[23] Angus Macleod．Optical Comings from Design through Manufacture[M]．浙江大学信息学院光学薄膜研究中心，译．2003．
[24] 郭永康．光学[M]．北京：高等教育出版社，2005
[25] 钟迪生．真空镀膜—光学材料的选择与应用[M]．沈阳：辽宁大学出版社，2001．
[26] 林永昌，卢维强．光学薄膜原理[M]．北京：国防工业出版社，1990．
[27] 秦跃利，高能武，吴云海．改进工艺提高薄膜附着力[J]．电子元件与材料，2000，1：26～27．
[28] 潘永强，卢进军 光学塑料真空镀膜附着力机理与工艺研究[J]．应用光学，2003，24(3)：32～34．
[29] 孙亦宁．中间层对薄膜附着力强度的改进[J]．真空于低温。1999，6：70～76．
[30] Mattox D M. Surface Effects on the Growth Adhesion and Propertics of Reactively Deposited Hard Coatings. Surface and Coatings Technology. 1996 81. 8～16.
[31] 谢致微，蒙继龙，王国庆．物理气相沉积薄膜的界面与附着力[J]．2001，5：203～208．
[32] 腾林，杨邦朝，崔红玲，杜晓松．金属薄膜附着性的改进[J]．电子元件与材料，2003，6：41～44．
[33] 赵峰．影响磁控阴极溅射法镀膜玻璃质量的原因及解决办法[J]．玻璃，1994，3：36～45．
[34] 王怡德．磁控溅射技术[M]．北京：北京中方盖德真空技术有限公司．
[35] 龚建华．镀膜玻璃膜层均匀性探讨[J]．真空，1996，2：20～24．
[36] 赵峰，商文库．镀膜玻璃的膜系特性及生产工艺控制[J]．玻璃，1996，6：37～42．
[37] 龚建华，张永胜，柳俊文．大面积玻璃基片磁控溅射真空镀膜简介(二)．真空，2006，3：1～4
[38] 杨友财．大面积玻璃基片磁控溅射镀膜膜层性质和特性的研究．硕士毕业论文，2007．
[39] 徐成海．真空工程技术[M]．北京：化学工业出版社，2006．
[40] 袁超．多层薄膜材料界面能的测定与分析[J]．硕士毕业论文，2003．
[41] L．B．Freund，S．Suresh著，卢磊译．薄膜材料—应力、缺陷的形成和表面演化[M]．北京：科学出版社，2007．
[42] Abermann. R, Measurements of the intrinsic stress in thin metal films, vacuum, 1990(41): 1279～1282.
[43] S Tamulevicius,Stress and strain in the vacuum deposited thin films,vacuum,Vacuum,1998,V5,No2,pl27～139.
[44] F.Spaepen,Interfaces and stresses in thin films,Acta mater 2000,V48,p31-42.
[45] D.W.Hoffman,J.A. Thornton,The compressive stress transition in Al,V,Zr,Nb and W metal films sputtered at low working pressures,Thin Solid Films. 1977,Vol .45,No,2,387～396.
[46] D.W.Hoffman,J.A.Thornton, Internal stresses in sputtered chromium, Thin Solid Films.l977,Vol.40,355～363.
[47]J.A.Thornton,D.W.Hoffman. Internal stresses in titanium,nickel,molybdenum,and tantalum films deposited by cylindrical magnetron sputtering, J.Vac. Sci. Technol,1977,Vol.14,No.1,164～168.
[48] J.A.Thornton, Magnetron sputtering: basic physics and application to cylindrical magnetrons,J.Vac. Sci. Technol,1978,Vol.14,No.2,171～177.
[49] D.W.Hoffman,J.A. Thornton, Effects of substrate orientation and rotation on internal stresses in sputteredmetal films, J.Vac. Sci.Technol, 1979,Vol.16,No.2,134.
[50] D.W.Hoffman,M.R. Gaerttner,Modification of evaporated chronmium by concurrent ion bombardment, J.Vac. Sci. Technol,1980,Vol.17,No.1,425～428.
[51] Wu C T, Kampwirth R T, Hafstrom J W, High-rate magnetron sputtering of high T_cNb_3S_n films, J.Vac. Sci. Technol,1977,Vol.14,No.1,134～137.
[52] H.Windischmann,Intrinsic stress in sputtered thin films, J.Vac. Sci.Technol,1991,A9(4),2431～2436.
[53] A.Entenberg,V. Lindbcrg, K.Fletcher, Stress measurement in sputtered copper films on flexible polyimide substrates, J.Vac. Sci. Technol, 1987,A5 , No.6,3373～3377.