DLC层厚度对CN_x/DLC多层膜结构及摩擦学性能的影响
|
摘要
采用直流磁控溅射法在硅基底上交替沉积类金刚石碳(DLC)和氮化碳(CNx)薄膜,制备了不同DLC层厚度的CNx/DLC纳米多层膜。使用X射线衍射、场发射扫描电子显微镜、X射线光电子谱、Raman光谱等测试手段表征了薄膜的微观组织形貌、化学成分和原子价键结构等。采用原位纳米压入技术、涂层附着力划痕仪、球盘式摩擦磨损试验机对薄膜的力学和摩擦学性能进行了测试。结果表明:所制备的CNx/DLC多层膜均为微晶或非晶结构,组织致密。随着DLC层厚度的减小,多层膜内sp3杂化键的含量先升高后下降,压应力由135 MPa增至538 MPa,结合力先上升后降低,而磨损率则呈相反变化趋势。多层膜在大气和真空中的摩擦因数约为0.17和0.15,DLC层厚度的影响很小。DLC层厚度为4.5 nm的多层膜的性能最佳,硬度可达44.1 GPa,最低磨损率为3.2×10-18m3/(N·m)。
CN_x/DLC nano-multilayer films with different diamond-like carbon(DLC) layer thicknesses were prepared via the alternate deposition of DLC layer and carbon nitride(CN_x) layer on silicon substrate by the DC magnetron sputtering technique. The microstructure, chemical composition and atomic valence bond structure of the films were characterized by X-ray diffraction, field emission scanning electron microscopy, X-ray photoelectron spectroscopy and Raman spectroscopy. The mechanical and tribological properties of the films were evaluated by in-situ nano-indentation technology, coating adhesion tester and ball-and-disk wear tester. The results show that the CN_x/DLC multilayer films are amorphous and dense structure. The content of sp3 hybrid bonds in the multilayer films firstly increases and then decreases, the compressive stress increases from 135 MPa to 538 MPa, and the bonding force firstly increases and then decreases, but the wear rate firstly decreases and then increases as the DLC layer thickness decreases. The friction coefficients of the multilayer films in atmosphere and in vacuum are 0.17 and 0.15, respectively, and the DLC layer thickness has a slight effect on the friction coefficient. The multilayer film with the DLC layer thickness of 4.5 nm has the optimum performance, having the maximum hardness of 44.1 GPa and the minimum wear rate of 3.2×10-18m3/(N·m).
CN_x/DLC nano-multilayer films with different diamond-like carbon(DLC) layer thicknesses were prepared via the alternate deposition of DLC layer and carbon nitride(CN_x) layer on silicon substrate by the DC magnetron sputtering technique. The microstructure, chemical composition and atomic valence bond structure of the films were characterized by X-ray diffraction, field emission scanning electron microscopy, X-ray photoelectron spectroscopy and Raman spectroscopy. The mechanical and tribological properties of the films were evaluated by in-situ nano-indentation technology, coating adhesion tester and ball-and-disk wear tester. The results show that the CN_x/DLC multilayer films are amorphous and dense structure. The content of sp3 hybrid bonds in the multilayer films firstly increases and then decreases, the compressive stress increases from 135 MPa to 538 MPa, and the bonding force firstly increases and then decreases, but the wear rate firstly decreases and then increases as the DLC layer thickness decreases. The friction coefficients of the multilayer films in atmosphere and in vacuum are 0.17 and 0.15, respectively, and the DLC layer thickness has a slight effect on the friction coefficient. The multilayer film with the DLC layer thickness of 4.5 nm has the optimum performance, having the maximum hardness of 44.1 GPa and the minimum wear rate of 3.2×10-18m3/(N·m).
引文
[1]CHENG Y,LU Y M,GUO Y L,et al.Multilayers diamond-like carbon film with germanium buffer layers by pulsed laser deposition[J].Surf Rev Lett,2017,24(2):306?312.
[2]刘军,毕凯,陈志刚,等.YG8衬底腐蚀处理对氮化碳薄膜摩擦学性能的影响[J].硅酸盐学报,2010,38(1):126?130.LIU Jun,BI Kai,CHEN Zhigang,et al.J Chin Ceram Soc,2010,38(1):126?130.
[3]ANDRIEVSKI R A.Nanostructured superhard films as typical nanomaterials[J].Surf Coat Technol,2007,201(13):6112?6116.
[4]谢红梅.类金刚石薄膜的摩擦学特性研究进展[J].表面技术,2011,40(3):90?93.XIE Hongmei.Surf Technol(in Chinese),2011,40(3):90?93.
[5]STOCK F,ANTONI F,LE N F.High performance diamond-like carbon layers obtained by pulsed laser deposition for conductive electrode applications[J].Appli Phys A:Mater Sci Process,2017,123(9):590?595.
[6]BOCIAGA Dorota,SOBCZYK-GUZENDA Anna,SZYMANSKIWitold.Diamond like carbon coatings doped by Si fabricated by a multi-target DC-RF magnetron sputtering method-Mechanical properties,chemical analysis and biological evaluation[J].Vacuum,2017,143:395?406.
[7]HAUERT R,THORWARTH K,THORWARTH G.An overview on diamond-like carbon coatings in medical applications[J].Surf Coat Technol,2013,233:119?130.
[8]GAYATHRI S,KUMAR N,KRISHNAN R,et al.Influence of transition metal doping on the tribological properties of pulsed laser deposited DLC films[J].Ceram Int,2015,41(1):1797?1805.
[9]FU Z Q,WANG C B,DU X J,et al.Tribological behaviors of W-doped DLC films[J].Key Eng Mater,2010,434/435:474?476.
[10]AMANOV A,WATABE T,TSUBOI R,et al.Fretting wear and fracture behaviors of Cr-doped and non-doped DLC films deposited on Ti-6Al-4V alloy by unbalanced magnetron sputtering[J].Tribol Int,2013,62(62):49?57.
[11]吴行阳,陈腾,葛宙,等.不同湿度条件下N、Si共掺杂DLC膜的摩擦学性能研究[J].摩擦学学报,2017,37(4):501?509.WU Xingyang,CHEN Teng,GE Zhou,et al.Tribology(in Chinese),2017,37(4):501?509.
[12]WANG J,MA J,HUANG W,et al.The investigation of the structures and tribological properties of F-DLC coatings deposited on Ti-6Al-4Valloys[J].Surf Coat Technol,2017,316:22?29.
[13]AKAIKE S,KOBAYASHI D,AONO Y,et al.Relationship between static friction and surface wettability of orthodontic brackets coated with diamond-like carbon(DLC),fluorine or silicone-doped DLCcoatings[J].Diamond Relat Mater,2016,61:109?114.
[14]DAI W,GAO X,LIU J,et al.Microstructure,mechanical property and thermal stability of diamond-like carbon coatings with Al,Cr and Si multi-doping[J].Diamond Relat Mater,2016,70:98?104.
[15]SUN L,GUO P,KE P,et al.Synergistic effect of Cu/Cr co-doping on the wettability and mechanical properties of diamond-like carbon films[J].Diamond Relat Mater,2016,68:1?9.
[16]JI L,LI H,ZHAO F,et al.Microstructure and mechanical properties of Mo/DLC nanocomposite films[J].Diamond Relat Mater,2008,17(11):1949?1954.
[17]XU Z,SUN H,LENG Y X,et al.Effect of modulation periods on the microstructure and mechanical properties of DLC/TiC multilayer films deposited by filtered cathodic vacuum arc method[J].Appl Surf Sci,2015,328:319?324.
[18]ZHANG W,TANAKA A,XU B S,et al.Study on the diamond-like carbon multilayer films for tribological application[J].Diamond Relat Mater,2005,14(8):1361?1367.
[19]林松盛,周克崧,代明江.类金刚石/碳化钨多层膜的制备及其结构[J].中国有色金属学报,2013(2):434?438.LIN Songsheng,ZHOU Kesong,DAI Mingjiang.Chin J Nonferrous Met(in Chinese),2013(2):434?438.
[20]沟引宁,孙鸿,黄楠,等.磁过滤真空弧源沉积技术制备C/C多层类金刚石膜及其摩擦磨损性能研究[J].摩擦学学报,2006(2):121?124.GOU Yining,SUN Hong,HUANG Nan,et al.Tribology(in Chinese),2006(2):121?124.
[21]LIU A Y,COHEN M L.Prediction of new low compressibility solids[J].Science,1989,245(4920):841?842.
[22]KIM Y J,BYUN T J,HAN J G.Tribological and mechanical behaviors of CrN/a-CNx superlattice thin films[J].Surf Coat Technol,2008,203(5):790?793.
[23]LI D,LIN X W,CHENG S C,et al.Structure and hardness studies of CNx/TiN nanocomposite coatings[J].Appl Phys Lett,1996,68(9):1211?1213.
[24]ZHENG X H,TU J P,SONG R G.Fabrication microstructure and tribological behavior of pulsed laser deposited a-CNx/TiN multilayer films[J].Surf Coat Technol,2010,205(3):902?908.
[25]HELLGREN N,HAASCH R T,SCHMIDT S,et al.Interpretation of X-ray photoelectron spectra of carbon-nitride thin films:New insights from in situ XPS[J].Carbon,2016,108:242?252.
[26]HOLLOWAY B C,KRAFT O,SHUH D K,et al.Interpretation of X-ray photoelectron spectra of elastic amorphous carbon nitride thin films[J].Appl Phys Lett,1999,74(22):3290?3292.
[27]JIN Y,SHIBATA T,MATSUDA Y,et al.Structural and bonding properties of carbon nitride films prepared by dc magnetron sputtering[J].Thin Solid Films,1999,345(1):18?22.
[28]ZHENG W T,GUO J H,SAKAMOTO Y,et al.Chemical bonding in carbon nitride films studied by X-ray spectroscopies[J].Diamond Relat Mater,2001,10(9):1897?1900.
[29]WANG X C,LI Z Q,WU P,et al.Annealing effects on the microstructure of amorphous carbon nitride films[J].Appl Surf Sci,2006,253(4):2087?2092.
[30]SHIN J K,LEE C S,LEE K R,et al.Effect of residual stress on the Raman-spectrum analysis of tetrahedral amorphous carbon films[J].Appl Phys Lett,2001,78(5):631?633.
[31]WANG X C,LI Z Q,WU P,et al.Structural and mechanical properties of facing-target sputtered amorphous CNx films[J].Diamond Relat Mater,2006,15(10):1732?1737.
[32]杨芳儿,陈占领,郑晓华,等.沉积偏压对脉冲激光沉积CNx薄膜结构和性能的影响[J].硅酸盐学报,2013,41(9):1265?1270.YANG Fanger,CHEN Zhanling,ZHENG Xiaohua,et al.J Chin Ceram Soc,2013,41(9):1265?1270.
[33]KATO M,MORI T,SCHWARTZ L H.Hardening by Spinodally Modulated Structure[J].Acta Metall,1980,28(3):285?290.
[34]GY?RGY E,NELEA V,MIHAILESCU I N,et al.Correlation between hardness and structure of carbon-nitride thin films obtained by reactive pulsed laser deposition[J].Thin Solid Films,2001,388(1/2):93?100.
[35]NI W,CHENG Y T,LUKITSCH M J,et al.Effects of the Ratio of hardness to Young's modulus on the friction and wear behavior of bilayer coatings[J].Appl Phys Lett,2004,85(18):4028?4030.
[36]LEYLAND A,MATTHEWS A.Design criteria for wear-resistant nanostructured and glassy-metal coatings[J].Surf Coat Technol,2004,177/178:317?324.
[37]GABRIEL S B,DE ALMEIDA L H,NUNES C A,et al.Maximisation of the ratio of microhardness to the Young's modulus of Ti-12Mo-13Nb alloy through microstructure changes[J].Mater Sci Eng C,2013,33(6):3319?3324.
[38]STEIER V F,PIRES M S T,DOCA T.The influence of diamond-like carbon and anodised aluminium oxide coatings on the surface properties of the SAE 305 aluminium alloy[J].J Braz Soc Mech Sci Eng,2018,40(2):41?52.
[39]KOVACI H,YETIM A F,?ZLEM Baran,et al.Tribological behavior of DLC films and duplex ceramic coatings under different sliding conditions[J].Ceram Int,2018,44(6):7151?7158.
[40]ZHOU F,WANG X,KATO K,et al.Friction and wear property of a-CNx coatings sliding against Si3N4 balls in water[J].Wear,2007,263(7-12):1253?1258.
[41]DENG X,HATTORI T,UMEHARA N,et al.Tribological properties of ta-CNx coatings with different nitrogen content under oil lubrication conditions[J].Thin Solid Films,2017,621:12?18.
[42]杨芳儿,常新新,郑晓华,等.CNx层厚度对DLC/CNx多层膜结构和力学性能的影响[J].中国表面工程,2018,31(2):66?74.YANG Fanger,CHANG Xinxin,ZHENG Xiaohua.Chin Surf Eng(in Chinese),2018,31(2):66?74.
[43]ERDEMIR A,ERYILMAZ O L,FENSKE G.Synthesis of diamondlike carbon films with superlow friction and wear properties[J].J Vac Sci Technol A:Vac Surf Films,2000,18(4):1987?1992.
[2]刘军,毕凯,陈志刚,等.YG8衬底腐蚀处理对氮化碳薄膜摩擦学性能的影响[J].硅酸盐学报,2010,38(1):126?130.LIU Jun,BI Kai,CHEN Zhigang,et al.J Chin Ceram Soc,2010,38(1):126?130.
[3]ANDRIEVSKI R A.Nanostructured superhard films as typical nanomaterials[J].Surf Coat Technol,2007,201(13):6112?6116.
[4]谢红梅.类金刚石薄膜的摩擦学特性研究进展[J].表面技术,2011,40(3):90?93.XIE Hongmei.Surf Technol(in Chinese),2011,40(3):90?93.
[5]STOCK F,ANTONI F,LE N F.High performance diamond-like carbon layers obtained by pulsed laser deposition for conductive electrode applications[J].Appli Phys A:Mater Sci Process,2017,123(9):590?595.
[6]BOCIAGA Dorota,SOBCZYK-GUZENDA Anna,SZYMANSKIWitold.Diamond like carbon coatings doped by Si fabricated by a multi-target DC-RF magnetron sputtering method-Mechanical properties,chemical analysis and biological evaluation[J].Vacuum,2017,143:395?406.
[7]HAUERT R,THORWARTH K,THORWARTH G.An overview on diamond-like carbon coatings in medical applications[J].Surf Coat Technol,2013,233:119?130.
[8]GAYATHRI S,KUMAR N,KRISHNAN R,et al.Influence of transition metal doping on the tribological properties of pulsed laser deposited DLC films[J].Ceram Int,2015,41(1):1797?1805.
[9]FU Z Q,WANG C B,DU X J,et al.Tribological behaviors of W-doped DLC films[J].Key Eng Mater,2010,434/435:474?476.
[10]AMANOV A,WATABE T,TSUBOI R,et al.Fretting wear and fracture behaviors of Cr-doped and non-doped DLC films deposited on Ti-6Al-4V alloy by unbalanced magnetron sputtering[J].Tribol Int,2013,62(62):49?57.
[11]吴行阳,陈腾,葛宙,等.不同湿度条件下N、Si共掺杂DLC膜的摩擦学性能研究[J].摩擦学学报,2017,37(4):501?509.WU Xingyang,CHEN Teng,GE Zhou,et al.Tribology(in Chinese),2017,37(4):501?509.
[12]WANG J,MA J,HUANG W,et al.The investigation of the structures and tribological properties of F-DLC coatings deposited on Ti-6Al-4Valloys[J].Surf Coat Technol,2017,316:22?29.
[13]AKAIKE S,KOBAYASHI D,AONO Y,et al.Relationship between static friction and surface wettability of orthodontic brackets coated with diamond-like carbon(DLC),fluorine or silicone-doped DLCcoatings[J].Diamond Relat Mater,2016,61:109?114.
[14]DAI W,GAO X,LIU J,et al.Microstructure,mechanical property and thermal stability of diamond-like carbon coatings with Al,Cr and Si multi-doping[J].Diamond Relat Mater,2016,70:98?104.
[15]SUN L,GUO P,KE P,et al.Synergistic effect of Cu/Cr co-doping on the wettability and mechanical properties of diamond-like carbon films[J].Diamond Relat Mater,2016,68:1?9.
[16]JI L,LI H,ZHAO F,et al.Microstructure and mechanical properties of Mo/DLC nanocomposite films[J].Diamond Relat Mater,2008,17(11):1949?1954.
[17]XU Z,SUN H,LENG Y X,et al.Effect of modulation periods on the microstructure and mechanical properties of DLC/TiC multilayer films deposited by filtered cathodic vacuum arc method[J].Appl Surf Sci,2015,328:319?324.
[18]ZHANG W,TANAKA A,XU B S,et al.Study on the diamond-like carbon multilayer films for tribological application[J].Diamond Relat Mater,2005,14(8):1361?1367.
[19]林松盛,周克崧,代明江.类金刚石/碳化钨多层膜的制备及其结构[J].中国有色金属学报,2013(2):434?438.LIN Songsheng,ZHOU Kesong,DAI Mingjiang.Chin J Nonferrous Met(in Chinese),2013(2):434?438.
[20]沟引宁,孙鸿,黄楠,等.磁过滤真空弧源沉积技术制备C/C多层类金刚石膜及其摩擦磨损性能研究[J].摩擦学学报,2006(2):121?124.GOU Yining,SUN Hong,HUANG Nan,et al.Tribology(in Chinese),2006(2):121?124.
[21]LIU A Y,COHEN M L.Prediction of new low compressibility solids[J].Science,1989,245(4920):841?842.
[22]KIM Y J,BYUN T J,HAN J G.Tribological and mechanical behaviors of CrN/a-CNx superlattice thin films[J].Surf Coat Technol,2008,203(5):790?793.
[23]LI D,LIN X W,CHENG S C,et al.Structure and hardness studies of CNx/TiN nanocomposite coatings[J].Appl Phys Lett,1996,68(9):1211?1213.
[24]ZHENG X H,TU J P,SONG R G.Fabrication microstructure and tribological behavior of pulsed laser deposited a-CNx/TiN multilayer films[J].Surf Coat Technol,2010,205(3):902?908.
[25]HELLGREN N,HAASCH R T,SCHMIDT S,et al.Interpretation of X-ray photoelectron spectra of carbon-nitride thin films:New insights from in situ XPS[J].Carbon,2016,108:242?252.
[26]HOLLOWAY B C,KRAFT O,SHUH D K,et al.Interpretation of X-ray photoelectron spectra of elastic amorphous carbon nitride thin films[J].Appl Phys Lett,1999,74(22):3290?3292.
[27]JIN Y,SHIBATA T,MATSUDA Y,et al.Structural and bonding properties of carbon nitride films prepared by dc magnetron sputtering[J].Thin Solid Films,1999,345(1):18?22.
[28]ZHENG W T,GUO J H,SAKAMOTO Y,et al.Chemical bonding in carbon nitride films studied by X-ray spectroscopies[J].Diamond Relat Mater,2001,10(9):1897?1900.
[29]WANG X C,LI Z Q,WU P,et al.Annealing effects on the microstructure of amorphous carbon nitride films[J].Appl Surf Sci,2006,253(4):2087?2092.
[30]SHIN J K,LEE C S,LEE K R,et al.Effect of residual stress on the Raman-spectrum analysis of tetrahedral amorphous carbon films[J].Appl Phys Lett,2001,78(5):631?633.
[31]WANG X C,LI Z Q,WU P,et al.Structural and mechanical properties of facing-target sputtered amorphous CNx films[J].Diamond Relat Mater,2006,15(10):1732?1737.
[32]杨芳儿,陈占领,郑晓华,等.沉积偏压对脉冲激光沉积CNx薄膜结构和性能的影响[J].硅酸盐学报,2013,41(9):1265?1270.YANG Fanger,CHEN Zhanling,ZHENG Xiaohua,et al.J Chin Ceram Soc,2013,41(9):1265?1270.
[33]KATO M,MORI T,SCHWARTZ L H.Hardening by Spinodally Modulated Structure[J].Acta Metall,1980,28(3):285?290.
[34]GY?RGY E,NELEA V,MIHAILESCU I N,et al.Correlation between hardness and structure of carbon-nitride thin films obtained by reactive pulsed laser deposition[J].Thin Solid Films,2001,388(1/2):93?100.
[35]NI W,CHENG Y T,LUKITSCH M J,et al.Effects of the Ratio of hardness to Young's modulus on the friction and wear behavior of bilayer coatings[J].Appl Phys Lett,2004,85(18):4028?4030.
[36]LEYLAND A,MATTHEWS A.Design criteria for wear-resistant nanostructured and glassy-metal coatings[J].Surf Coat Technol,2004,177/178:317?324.
[37]GABRIEL S B,DE ALMEIDA L H,NUNES C A,et al.Maximisation of the ratio of microhardness to the Young's modulus of Ti-12Mo-13Nb alloy through microstructure changes[J].Mater Sci Eng C,2013,33(6):3319?3324.
[38]STEIER V F,PIRES M S T,DOCA T.The influence of diamond-like carbon and anodised aluminium oxide coatings on the surface properties of the SAE 305 aluminium alloy[J].J Braz Soc Mech Sci Eng,2018,40(2):41?52.
[39]KOVACI H,YETIM A F,?ZLEM Baran,et al.Tribological behavior of DLC films and duplex ceramic coatings under different sliding conditions[J].Ceram Int,2018,44(6):7151?7158.
[40]ZHOU F,WANG X,KATO K,et al.Friction and wear property of a-CNx coatings sliding against Si3N4 balls in water[J].Wear,2007,263(7-12):1253?1258.
[41]DENG X,HATTORI T,UMEHARA N,et al.Tribological properties of ta-CNx coatings with different nitrogen content under oil lubrication conditions[J].Thin Solid Films,2017,621:12?18.
[42]杨芳儿,常新新,郑晓华,等.CNx层厚度对DLC/CNx多层膜结构和力学性能的影响[J].中国表面工程,2018,31(2):66?74.YANG Fanger,CHANG Xinxin,ZHENG Xiaohua.Chin Surf Eng(in Chinese),2018,31(2):66?74.
[43]ERDEMIR A,ERYILMAZ O L,FENSKE G.Synthesis of diamondlike carbon films with superlow friction and wear properties[J].J Vac Sci Technol A:Vac Surf Films,2000,18(4):1987?1992.
© 2004-2018 中国地质图书馆版权所有 京ICP备05064691号 京公网安备11010802017129号 地址：北京市海淀区学院路29号 邮编：100083 电话：办公室：(+86 10)66554848；文献借阅、咨询服务、科技查新：66554700 |