用PECVD制备类金刚石膜的研究
摘要
本文以丁烷(C_4H_(10))和氩气(Ar)为源气体,利用射频等离子体增强化学气相沉积法(RF-PECVD)在硅衬底上制备了类金刚石(DLC)薄膜。通过调整射频功率、基板偏压、衬底温度和源气体流量等工艺参数,沉积出了质量较好的类金刚石膜。并研究了工艺参数对薄膜沉积速率、硬度和表面粗糙度的影响。
通过Raman光谱和傅里叶变换红外光谱(FTIR)分析了薄膜的结构,所制备的薄膜符合DLC膜的典型特征;用原子力显微镜对薄膜的表面形貌进行了观察,薄膜为表面致密、平整的非晶态结构;通过纳米压痕仪测试了薄膜的硬度;Taylor轮廓仪测试了薄膜的表面粗糙度。通过测试结果分析讨论了工艺参数对DLC薄膜性能的影响。
In this paper, we deposited diamond-like carbon (DLC) films on the Si substrate using butane (C_4H_(10)) and argon (Ar) as source gases by radio frequency plasma enhanced chemical vapor deposition (RF-PECVD).Through adjusting technical parameters such as radio frequency power, bias voltage, substrate temperature and the flow rate of the source gase, we obtained high quality DLC films. The effect of technical parameters on deposition rate, hardness and surface roughness of DLC films were researched.
The microstructure of the films were studied with Raman spectroscopy and FTIR. The morphology of the films were studied with Atomic Force Microscope(AFM).The thin film was dense, smooth and structurally amorphous. The hardness and surface roughness of the films were measured by nano-indenter and Taylor profilometer. Finally the effect of technical parameters on the properties of DLC films were discussed with measure results.
通过Raman光谱和傅里叶变换红外光谱(FTIR)分析了薄膜的结构,所制备的薄膜符合DLC膜的典型特征;用原子力显微镜对薄膜的表面形貌进行了观察,薄膜为表面致密、平整的非晶态结构;通过纳米压痕仪测试了薄膜的硬度;Taylor轮廓仪测试了薄膜的表面粗糙度。通过测试结果分析讨论了工艺参数对DLC薄膜性能的影响。
In this paper, we deposited diamond-like carbon (DLC) films on the Si substrate using butane (C_4H_(10)) and argon (Ar) as source gases by radio frequency plasma enhanced chemical vapor deposition (RF-PECVD).Through adjusting technical parameters such as radio frequency power, bias voltage, substrate temperature and the flow rate of the source gase, we obtained high quality DLC films. The effect of technical parameters on deposition rate, hardness and surface roughness of DLC films were researched.
The microstructure of the films were studied with Raman spectroscopy and FTIR. The morphology of the films were studied with Atomic Force Microscope(AFM).The thin film was dense, smooth and structurally amorphous. The hardness and surface roughness of the films were measured by nano-indenter and Taylor profilometer. Finally the effect of technical parameters on the properties of DLC films were discussed with measure results.
引文
[1]J.H.Ouyang,S.Sasaki.Friction and Wear Characteristics of A Ti-containing Diamond-like Carbon Coating with an SRV Tester at High Contact Load and Elevated Temperature.Surf.Coat.Technol.2005,(195):234-244.
[2]J.S.Wang,Y.Sugimura,A.G.Evans,W.K.Tredway.Themechanicalperformance of DLC films on steel substrates[J],Thin Solid Films,1998,325:163-174.
[3]J.Robertson.Plasma-deposited diamond-like carbon and related materials[J],Adv.Phys,1986,(35):317-321
[4]卫中山,左敦稳,类金刚石膜的制备及应用,航空精密制造技术,2004,(40):20-23
[5]K.Y.Li,Z.F.Zhou,C.Y.Chan,I.Bello,C.S.Lee,S.T.Lee.Mechanical andtribological properties of diamond-like carbon films prepared on steel byECR-CVD process[J],Diamond and Related Material,2001,10:1855-1861.
[6]H.A麦克劳德.光学薄膜技术[M].周九林译.国防工业出版社,1974,1-266
[7]O.Glozman,A.Hoffman.Adhesion improvement of diamond films on steelsubstrates using chromium nitride interlayers[J],Diamond Rela.Mater.,1997,6:796-801.
[8]R.Hauert.A Review of Modified DLC Coatings for Biological Applications.Diamond Relat.Mater.2003,12(2-3):583.
[9]J.Robertson.Diamond-like amorphous carbon[J],Material Science andEngineering,2002,37:129-281.
[10]宋继鑫.国外光学薄膜的应用和真空镀膜技术[J].光学技术.1994,(1):32-39
[11]林永昌,卢维强.光学薄膜原理[M].国防工业出版社,1999:332-334
[12]Da-Yung WangU,Ko-Wei Weng,Shi-Yao Hwang.Study on metal-dopeddiamond-like carbon films synthesized by cathodic arc evaporation[J],Diamond and Related Materials,2000,9:1762-1766.
[13]R.Gilmore,R.Hauert.Control of the Tribological Moisture Sensitivity of Diamond-like Carbon Films by Alloying with F,Ti or Si.Thin Solid Films.2001,(398):199.
[14]Lettington,Alan H.Applications of diamond-like carbon thin films[J],Carbon,1998,36(5-6):555-560
[15]R.Gilmore,R.Hauert.Comparative Study of The Tribological Moisture Sensitivity of Si-free and Si-containing Diamond-like Carbon Films.Surf.Coat.Technol.2000,(133):437.
[16]Schiffmann Kirsten I,Hieke Andreas.Analysis of microwear experiments on thin DLC coatings:friction,wear and plastic deformation[J].Wear,2003,254(5-6):565-572
[17]M.Grischke,K.Bewilogua,K.Trojian,H.Dimigen.Application-oriented Modifications of Deposition Processes for Diamond-like-carbon-based Coatings.Surf.Coat.Technol.1996,(74-75):739.
[18]K.Bewilogua,C.V.Cooper,C.Specht,J.Schroeder,R.Wittorf,M.Grischke.Effect of Target Material on Deposition and Properties of Metal-containing DLC(Me-DLC) Coatings.Surf.Coat.Technol.2000,(132):275.
[19]M.Pandey,D.Bhatacharyya,D.S.Patil,K.Ramachandran,N.Venkatramani.Diamond-like Carbon Coatings:AFM and Ellipsometric Studies.Surface and Coatings Technology,2004,(182):24-34.
[20]L.S.Stephens,Y.Liu,E.I.Meletis.Finite Element Analysis of the InitialYielding Behavior of a Hard Coating/Substrate System with Functionally Graded Interface under Indentation and Friction.Journal of Tribology-Transactions of the ASME 2000,122(2)381.
[21]A.Shirakura,M.Nakaya,Y.Koga,H.Kodama,T.Hasebe,T.Suzuki.Diamond-like carbon films for PET bottles and medical applications.Thin Solid Films.2006,494(1-2):84-91
[22]J.Xu,H.Kousaka,N.Umehara,D.Diao.Plasma properties of a new surface-wave-sustained plasma source under the conditions of depositing DLC films.Surface and Coatings Technology.In Press,Corrected Proof,Available online 18January 2006
[23]唐伟忠.薄膜材料制备原理、技术及应用[M].北京:冶金工业出版社.2003,32-40
[24]衰镇海,邓其森,罗广南,谢致薇,郑健红.类金刚石膜的制备、性能和应用[J].材料科学与-工程1994,4:12
[25]贺亚敏,黄培林,uR晓迎.新型生物医学材料一类金刚石膜的研究进展.[J].国外医学生物医学工程分册2002,2:25
[26]袁镇海,付志强,邓其森,硬质合金刀具的类金刚石涂层的研究[J],广东有色金属学报,2001,(11):55-58
[27]Kawata K.Development of mass-production-type plasma chemical vapor deposition equipment and its application to various dies[J].Surf.Coat.Technol,1992,54-55:604-608
[28]Z.H.Xie,R.Singh,A.Bendavid,P.J.Martin,P.R.Munroe,M.Hoffman.Contact Damage Evolution in a Diamond-like Carbon(DLC) Coating on a Stainless Steel Substrate.Thin Solid Films,In Press,Corrected Proof,Available online 23February 2006.
[29]M.Hans,R.Buechel,M.Grischke,R.Hobi,M.Zaech.High-volume PVD Coating of Precision Components of Large Volumes at Low Process Costs.Surf.Coat.Technol.2000,(123):288.
[30]H.K.普尔克尔.玻璃镀膜[M].仲永安译.科学出版社,1988:70-76
[31]A.Soum-Glaude,L.Thomas,E.Tomasella.Amorphous silicon carbide coatings grown by low frequency PACVD:Structural and mechanical description.Surface and Coatings Technology.2006,200(22-23):6425-6429
[32]C.Fernandez-Ramos,J.C.Sachez-Lopez,M.Belin,C.Donnet,L.Ponsonnet,A.Fernandez.Tribological behaviour and chemical characterisation of Si-free and Si-containing carbon nitride coatings.Diamond and Related Materials.2002,11(2):169-175
[33]柳襄怀.离子束增强沉积薄膜合成及其在材料表面优化中的应用.上海有色金属.1994,(2):65-66
[34]徐军,邓新绿,张家良等.双放电腔微波-ECR等离子体源增强磁控溅射沉积技术[J].大连理工大学学报.2001,41(3):275-278.
[35]马腾才,胡希伟,陈银华.等离子体物理原理[M].中国科学技术大学出版社.1988,1-2
[36]彭国贤.气体放电-等离子体物理的应用[M].上海:知识出版社,1988.65-72
[37]李刘合,夏立芳,马欣新,孙跃.真空阴极弧离子镀类金刚石碳膜.哈尔滨工业大学学报.1999,(1):97.
[38]Liu A Y,et al.Prediction of new low compressibility solids[J],Science,1989,(245):841-842
[39]M.Buttarello.Quality specification in haematology:the automated blood cell count.Clinica Chimica Acta.2004,346(1):45-54
[40]郑伟涛,薄膜材料与薄膜技术[M].北京:化学工业出版社,2004.
[41]孙杏凡.等离子体及其应用[M].北京:高等教育出版社,1982,162-174
[42]T.W.Scharf,I.L.Singer.Thickness of Diamond-like Carbon Coatings Quantified with Raman Spectroscopy.Thin Solid Films,2003,(440):138-144.
[43]金佑民,樊友三.低温等离子体物理基础[M].北京:清华大学出版社,1983.156-184
[44]张光华.等离子体与成膜基础[M].北京:国防工业出版社,1994.58-126
[45]夏立芳,孙跃,马欣新.等离子体湮没离子注入.金属热处理.1995,(2):3.
[46]A.A.Voevodin,J.S.Zabinski.Nanocomposite and nanostructured tribological materials for space applications.Composites Science and Technology.2005,65(5)
[47]S.R.P.Silva,J.D.Carey,X.Guo,W.M.Tsang,C.H.P.Poa.Electron field emission from carbon-based materials.Thin Solid Films.2005,482(1-2):79-85
[48]李之杰,潘正瑛:离子束辅助沉积对类金刚石膜结构影响的计算机模拟.物理学报.2005,(54):2233.
[49]杨烈宇.材料表面薄膜技术[M].北京:人民交通出版社,1991,45-63
[50]程宇航,吴一平,陈建国,乔学亮,谢长生.类金刚石膜的结构与性能研究.[J].硅酸盐学报.1997,4:25
[51]E.Konca,Y.-T.Cheng,A.M.Weiner,J.M.Dasch,A.T.Alpas.Elevated temperature tribological behavior of non-hydrogenated diamond-like carbon coatings against 319 aluminum alloy.Surface and Coatings Technology.2006,200(12-13):3996-4005
[52]P.Mosaner,M.Bonelli,A.Miotello.Pulsed laser deposition of diamond-like carbon films:reducing internal stress by thermal annealing.Applied Surface Science.2003,208-209:561-565
[53]田中章浩.类金刚石薄膜和金刚石薄膜的最新制备技术与各种特性.珠宝科技,2004,(6):23.
[54]李刘合,夏立芳,张海泉,张彦华,周志敏.类金刚石碳膜的摩擦学特性及其研究进展.[J].摩擦学报.2001,1:21
[55]邵淑英,范正修,范瑞瑛等.薄膜应力的研究[J].激光与光电子学进展,2005,42:73-78
[2]J.S.Wang,Y.Sugimura,A.G.Evans,W.K.Tredway.Themechanicalperformance of DLC films on steel substrates[J],Thin Solid Films,1998,325:163-174.
[3]J.Robertson.Plasma-deposited diamond-like carbon and related materials[J],Adv.Phys,1986,(35):317-321
[4]卫中山,左敦稳,类金刚石膜的制备及应用,航空精密制造技术,2004,(40):20-23
[5]K.Y.Li,Z.F.Zhou,C.Y.Chan,I.Bello,C.S.Lee,S.T.Lee.Mechanical andtribological properties of diamond-like carbon films prepared on steel byECR-CVD process[J],Diamond and Related Material,2001,10:1855-1861.
[6]H.A麦克劳德.光学薄膜技术[M].周九林译.国防工业出版社,1974,1-266
[7]O.Glozman,A.Hoffman.Adhesion improvement of diamond films on steelsubstrates using chromium nitride interlayers[J],Diamond Rela.Mater.,1997,6:796-801.
[8]R.Hauert.A Review of Modified DLC Coatings for Biological Applications.Diamond Relat.Mater.2003,12(2-3):583.
[9]J.Robertson.Diamond-like amorphous carbon[J],Material Science andEngineering,2002,37:129-281.
[10]宋继鑫.国外光学薄膜的应用和真空镀膜技术[J].光学技术.1994,(1):32-39
[11]林永昌,卢维强.光学薄膜原理[M].国防工业出版社,1999:332-334
[12]Da-Yung WangU,Ko-Wei Weng,Shi-Yao Hwang.Study on metal-dopeddiamond-like carbon films synthesized by cathodic arc evaporation[J],Diamond and Related Materials,2000,9:1762-1766.
[13]R.Gilmore,R.Hauert.Control of the Tribological Moisture Sensitivity of Diamond-like Carbon Films by Alloying with F,Ti or Si.Thin Solid Films.2001,(398):199.
[14]Lettington,Alan H.Applications of diamond-like carbon thin films[J],Carbon,1998,36(5-6):555-560
[15]R.Gilmore,R.Hauert.Comparative Study of The Tribological Moisture Sensitivity of Si-free and Si-containing Diamond-like Carbon Films.Surf.Coat.Technol.2000,(133):437.
[16]Schiffmann Kirsten I,Hieke Andreas.Analysis of microwear experiments on thin DLC coatings:friction,wear and plastic deformation[J].Wear,2003,254(5-6):565-572
[17]M.Grischke,K.Bewilogua,K.Trojian,H.Dimigen.Application-oriented Modifications of Deposition Processes for Diamond-like-carbon-based Coatings.Surf.Coat.Technol.1996,(74-75):739.
[18]K.Bewilogua,C.V.Cooper,C.Specht,J.Schroeder,R.Wittorf,M.Grischke.Effect of Target Material on Deposition and Properties of Metal-containing DLC(Me-DLC) Coatings.Surf.Coat.Technol.2000,(132):275.
[19]M.Pandey,D.Bhatacharyya,D.S.Patil,K.Ramachandran,N.Venkatramani.Diamond-like Carbon Coatings:AFM and Ellipsometric Studies.Surface and Coatings Technology,2004,(182):24-34.
[20]L.S.Stephens,Y.Liu,E.I.Meletis.Finite Element Analysis of the InitialYielding Behavior of a Hard Coating/Substrate System with Functionally Graded Interface under Indentation and Friction.Journal of Tribology-Transactions of the ASME 2000,122(2)381.
[21]A.Shirakura,M.Nakaya,Y.Koga,H.Kodama,T.Hasebe,T.Suzuki.Diamond-like carbon films for PET bottles and medical applications.Thin Solid Films.2006,494(1-2):84-91
[22]J.Xu,H.Kousaka,N.Umehara,D.Diao.Plasma properties of a new surface-wave-sustained plasma source under the conditions of depositing DLC films.Surface and Coatings Technology.In Press,Corrected Proof,Available online 18January 2006
[23]唐伟忠.薄膜材料制备原理、技术及应用[M].北京:冶金工业出版社.2003,32-40
[24]衰镇海,邓其森,罗广南,谢致薇,郑健红.类金刚石膜的制备、性能和应用[J].材料科学与-工程1994,4:12
[25]贺亚敏,黄培林,uR晓迎.新型生物医学材料一类金刚石膜的研究进展.[J].国外医学生物医学工程分册2002,2:25
[26]袁镇海,付志强,邓其森,硬质合金刀具的类金刚石涂层的研究[J],广东有色金属学报,2001,(11):55-58
[27]Kawata K.Development of mass-production-type plasma chemical vapor deposition equipment and its application to various dies[J].Surf.Coat.Technol,1992,54-55:604-608
[28]Z.H.Xie,R.Singh,A.Bendavid,P.J.Martin,P.R.Munroe,M.Hoffman.Contact Damage Evolution in a Diamond-like Carbon(DLC) Coating on a Stainless Steel Substrate.Thin Solid Films,In Press,Corrected Proof,Available online 23February 2006.
[29]M.Hans,R.Buechel,M.Grischke,R.Hobi,M.Zaech.High-volume PVD Coating of Precision Components of Large Volumes at Low Process Costs.Surf.Coat.Technol.2000,(123):288.
[30]H.K.普尔克尔.玻璃镀膜[M].仲永安译.科学出版社,1988:70-76
[31]A.Soum-Glaude,L.Thomas,E.Tomasella.Amorphous silicon carbide coatings grown by low frequency PACVD:Structural and mechanical description.Surface and Coatings Technology.2006,200(22-23):6425-6429
[32]C.Fernandez-Ramos,J.C.Sachez-Lopez,M.Belin,C.Donnet,L.Ponsonnet,A.Fernandez.Tribological behaviour and chemical characterisation of Si-free and Si-containing carbon nitride coatings.Diamond and Related Materials.2002,11(2):169-175
[33]柳襄怀.离子束增强沉积薄膜合成及其在材料表面优化中的应用.上海有色金属.1994,(2):65-66
[34]徐军,邓新绿,张家良等.双放电腔微波-ECR等离子体源增强磁控溅射沉积技术[J].大连理工大学学报.2001,41(3):275-278.
[35]马腾才,胡希伟,陈银华.等离子体物理原理[M].中国科学技术大学出版社.1988,1-2
[36]彭国贤.气体放电-等离子体物理的应用[M].上海:知识出版社,1988.65-72
[37]李刘合,夏立芳,马欣新,孙跃.真空阴极弧离子镀类金刚石碳膜.哈尔滨工业大学学报.1999,(1):97.
[38]Liu A Y,et al.Prediction of new low compressibility solids[J],Science,1989,(245):841-842
[39]M.Buttarello.Quality specification in haematology:the automated blood cell count.Clinica Chimica Acta.2004,346(1):45-54
[40]郑伟涛,薄膜材料与薄膜技术[M].北京:化学工业出版社,2004.
[41]孙杏凡.等离子体及其应用[M].北京:高等教育出版社,1982,162-174
[42]T.W.Scharf,I.L.Singer.Thickness of Diamond-like Carbon Coatings Quantified with Raman Spectroscopy.Thin Solid Films,2003,(440):138-144.
[43]金佑民,樊友三.低温等离子体物理基础[M].北京:清华大学出版社,1983.156-184
[44]张光华.等离子体与成膜基础[M].北京:国防工业出版社,1994.58-126
[45]夏立芳,孙跃,马欣新.等离子体湮没离子注入.金属热处理.1995,(2):3.
[46]A.A.Voevodin,J.S.Zabinski.Nanocomposite and nanostructured tribological materials for space applications.Composites Science and Technology.2005,65(5)
[47]S.R.P.Silva,J.D.Carey,X.Guo,W.M.Tsang,C.H.P.Poa.Electron field emission from carbon-based materials.Thin Solid Films.2005,482(1-2):79-85
[48]李之杰,潘正瑛:离子束辅助沉积对类金刚石膜结构影响的计算机模拟.物理学报.2005,(54):2233.
[49]杨烈宇.材料表面薄膜技术[M].北京:人民交通出版社,1991,45-63
[50]程宇航,吴一平,陈建国,乔学亮,谢长生.类金刚石膜的结构与性能研究.[J].硅酸盐学报.1997,4:25
[51]E.Konca,Y.-T.Cheng,A.M.Weiner,J.M.Dasch,A.T.Alpas.Elevated temperature tribological behavior of non-hydrogenated diamond-like carbon coatings against 319 aluminum alloy.Surface and Coatings Technology.2006,200(12-13):3996-4005
[52]P.Mosaner,M.Bonelli,A.Miotello.Pulsed laser deposition of diamond-like carbon films:reducing internal stress by thermal annealing.Applied Surface Science.2003,208-209:561-565
[53]田中章浩.类金刚石薄膜和金刚石薄膜的最新制备技术与各种特性.珠宝科技,2004,(6):23.
[54]李刘合,夏立芳,张海泉,张彦华,周志敏.类金刚石碳膜的摩擦学特性及其研究进展.[J].摩擦学报.2001,1:21
[55]邵淑英,范正修,范瑞瑛等.薄膜应力的研究[J].激光与光电子学进展,2005,42:73-78