低转速下多弧离子镀制备的Mo-Ti-Al-N超晶格硬质涂层的微结构及背散射谱分析
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摘要
目的研究低基片转速对纳米多层膜微结构和性能的影响。方法采用阴极多弧离子镀技术在单晶硅基片上沉积制备了MoTiAlN/MoN/Mo纳米复合结构涂层,借助X射线衍射仪(XRD)、扫描电镜(SEM)、透射电镜(TEM)、背散射谱(RBS)和纳米硬度计,分别对样品的物相、形貌、组分和硬度进行表征分析。结果 XRD显示不同转速下制备的涂层的物相结构主要为六角密排结构的Mo N和面心立方(Ti,Al)N,较高基片转速下涂层的结晶性较好。SEM和TEM图像证实,2 r/min基片转速下的目标涂层具有平均调制周期26 nm的Ti AlN/MoN超晶格结构,总厚度为1.15μm,且界面清晰。纳米显微硬度测试表明,低基片转速下,涂层硬度和杨氏模量分别达到(30±2)GPa和(500±30)GPa。结论不同能量的~7Li~(2+)离子卢瑟福背散射谱结合SIMNRA拟合程序,可定量评估该超晶格结构涂层的原子百分比、每个子层的物理厚度及调制周期,这为纳米多层膜的微结构表征提供了一种有效的分析手段。
The work aims to study the impact of low substrate rotation speed on microstructure and physical properties of nanostructured multilayer. MoTiAlN/MoN/Mo composite coatings were deposited on silicon substrates by cathodic multi-arc ion plating, and the phase structure, morphology, component and nanohardness of coatings species were characterized by X-ray diffraction, scanning electron microscopy, transmission electron microscopy, Rutherford backscattering spectroscopy and nanohardness tester. XRD results indicated that the coatings deposited at various substrate rotation speeds comprised hcp-MoN and fcc-(Ti,Al)N phases and the crystallinity was better at higher substrate rotation speed. SEM and TEM images confirmed that the mean modulation period and total physical thickness of superlattice TiAlN/MoN coatings with a sharp interface deposited at 2 r/min were 26 nm and 1.15 μm, respectively and the interface was clear. The nanohardness and Young modulus were up to(30±2) GPa and(500±30) GPa, respectively. RBS along with SIMNRA program proves to be a good method to evaluate the atomic concentrations, physical thicknesses of individual sublayers as well as the modulation periods of superlattice coatings quantitatively and provide reliable characterization for nanomultilayers.
The work aims to study the impact of low substrate rotation speed on microstructure and physical properties of nanostructured multilayer. MoTiAlN/MoN/Mo composite coatings were deposited on silicon substrates by cathodic multi-arc ion plating, and the phase structure, morphology, component and nanohardness of coatings species were characterized by X-ray diffraction, scanning electron microscopy, transmission electron microscopy, Rutherford backscattering spectroscopy and nanohardness tester. XRD results indicated that the coatings deposited at various substrate rotation speeds comprised hcp-MoN and fcc-(Ti,Al)N phases and the crystallinity was better at higher substrate rotation speed. SEM and TEM images confirmed that the mean modulation period and total physical thickness of superlattice TiAlN/MoN coatings with a sharp interface deposited at 2 r/min were 26 nm and 1.15 μm, respectively and the interface was clear. The nanohardness and Young modulus were up to(30±2) GPa and(500±30) GPa, respectively. RBS along with SIMNRA program proves to be a good method to evaluate the atomic concentrations, physical thicknesses of individual sublayers as well as the modulation periods of superlattice coatings quantitatively and provide reliable characterization for nanomultilayers.
引文
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[23]刘丹,韩滨,闫少健,等.多弧离子镀制备TiN/TiBN纳米复合涂层的结构和性能[J].中国表面工程,2014,27(5):102-108.LIU Dan,HAN Bin,YAN Shao-jian,et al.Structure and mechanical properties of TiN/TiB nanocomposite coatings deposited by multi-arc plasma deposition[J].Chinese surface engineering,2014,27(5):102-108.
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[25]KIM S K,LE V V,VINH P V,et al.Effect of cathode arc current and bias voltage on the mechanical properties of CrAlSiN thin films[J].Surface and coatings technology,2008,202(22-23):5400-5404.
[26]FUKUMOTO N,EZURA H,YAMAMOTO K,et al.Effects of bilayer thickness and post-deposition annealing on the mechanical and structural properties of(Ti,Cr,Al)N/(Al,Si)N multilayer coatings[J].Surface and coatings Technology,2009,203(10-11):1343-1348.
[27]WANG Y Q,NASTASI M.Handbook of modern ion beam materials analysis[M].2nd edition.Warrendale:Materials Research Society Press,2009.
[28]MAYER M.SIMNRA,a simulation program for the analysis of NRA,RBS and ERDA[C]//AIP conference proceedings.Seoul:IOP institute of physics publishing ltd,1999:541-544.
[29]KOTAI E.Computer methods for analysis and simulation of RBS and ERDA spectra[J].Nuclear instruments and methods in physics research section B:Beam interactions with materials and atoms,1994,85(1):588-596.
[2]张山山,王锦标,苏永要.纳米多层膜的研究现状[J].材料导报,2014,28(11):147-154.ZHANG Shan-shan,WANG Jin-biao,SU Yong-yao.Current research status of nano-multilayer films[J].Materials review,2014,28(11):147-154.
[3]BARNETT S A,SHINN M.Plastic and elastic properties of compositionally modulated thin films[J].Annual review of materials science,1994,24(1):481-511.
[4]KNOTEK O,LOFFLER F,KRAMER G.Multicomponent and multilayer physically vapour deposited coatings for cutting tools[J].Surface&coatings technology,1992,54-55(1):241-248.
[5]SUBRAMANIAN C,STRAFFORD K N.Review of multicomponent and multilayer coatings for tribological applications[J].Wear,1993,165(1):85-95.
[6]BELOV D S,VOLKHONSKY A O,BLINKOV I V,et al.Multilayer nanostructured wear-resistant coatings with increased thermal stability,adapted to varying friction conditions[J].Proceedings of the international conference nanomaterials:Applications and properties,2013,2(2):02FNC10.
[7]陈德军.TiN/AlN纳米多层膜的制备与性能研究[D].广州:广东工业大学,2007.CHEN De-jun.A study on preparation and mechanical property of Ti N/AlN nanomultilayers[D].Guangzhou:Guangdong University of Technology,2007.
[8]张文勇,孙德恩,裴晨蕊,等.调制周期对Cr Al N/Zr N纳米多层膜韧性的影响[J].表面技术,2016,45(1):55-61.ZHANG Wen-yong,SUN De-en,PEI Chen-rui,et al.Effect of modulation period on toughness of CrAlN/ZrN Nanomultilayer films[J].Surface technology,2016,45(1):55-61.
[9]YU D,WANG C,CHENG X,et al.Optimization of hybrid PVD process of TiAlN coatings by Taguchi method[J].Applied surface science,2008,255(5):1865-1869.
[10]YOUSAF M I,PELENOVICH V O,YANG B,et al.Effect of bilayer period on structural and mechanical properties of nanocomposite TiAlN/MoN multilayer films synthesized by cathodic arc ion-plating[J].Surface&coatings technology,2015,282:94-102.
[11]朱雪婷,孙勇,郭中正,等.射频磁控溅射沉积Al/Al2O3纳米多层膜的结构及性能[J].真空科学与技术学报,2013,33(5):477-482.ZHU Xue-ting,SUN Yong,GUO Zhong-zheng,et al.Microstructures and properties of magnetron sputtered Al/Al2O3 multilayers[J].Chinese journal of vacuum science and technology,2013,33(5):477-482.
[12]KONG M,YUE J L,LI G Y.Research development of hard ceramic nano-multilayer films[J].Journal of inorganic materials,2010,25(2):113-119.
[13]LEE D K,LEE S H,LEE J J.The structure and mechanical properties of multilayer TiN/(Ti0.5Al0.5)N coatings deposited by plasma enhanced chemical vapor deposition[J].Surface and coatings technology,2003,169:433-437.
[14]HELMERSSON U,TODOROVA S,BARNETT S A,et al.Growth of single-crystal TiN/VN stained-layer superlattices with extremely high mechanical hardness[J].Journal of applied physics,1987,62(2):481-486.
[15]刘超卓.分析薄膜厚度与成分的卢瑟福背散射分析[J].理化检验(物理分册),2010,46(7):436-440.LIU Chao-zhuo.Rutherford backscattering technique for analysing the thickness and composition of thin films[J].Physical testing and chemical analysis(part A:Physical testing),2010,46(7):436-440.
[16]TAVARES C J,REBOUTA L,ALVES E,et al.Study of roughness in Ti0.4Al0.6N/Mo multilayer structures[J].Nuclear instruments and methods in physics research section B:Beam interactions with materials and atoms,2002,188(1-4):90-95.
[17]TAVARES C J,REBOUTA L,RIVIERE J P,et al.Atomic environment and interfacial structural order of TiAlN/Mo multilayers[J].Surface and coatings technology,2004187:393-398.
[18]CHU W K,MAYER J W,NICOLET M A.Backscattering spectrometry[M].New York:Academic Press,1978.
[19]DISERENS M,PATSCHEIDER J,LEVY F.Improving the properties of titanium nitride by incorporation of silicon[J].Surface and coatings technology,1998,108-109:241-246.
[20]ZHANG S H,WU W W,CHEN W L,et al.Structural optimisation and synthesis of multilayers and nanocomposite AlCrTiSiN coatings for excellent machinability[J]Surface and coatings technology,2015,277:23-29.
[21]CHEN M H,CHEN W L,CAI F,et al.Structural evolution and electrochemical behaviors of multilayer Al-CrSi-N coatings[J].Surface and coatings technology,2016,296:33-39.
[22]TRITREMMEL C,DANIE R,LECHTHALER M,et al.Influence of Al and Si content on structure and mechanical properties of arc evaporated Al-Cr-Si-N thin films[J].Thin solid films,2013,534:403-409.
[23]刘丹,韩滨,闫少健,等.多弧离子镀制备TiN/TiBN纳米复合涂层的结构和性能[J].中国表面工程,2014,27(5):102-108.LIU Dan,HAN Bin,YAN Shao-jian,et al.Structure and mechanical properties of TiN/TiB nanocomposite coatings deposited by multi-arc plasma deposition[J].Chinese surface engineering,2014,27(5):102-108.
[24]CHU X,BARNETT S A,WONG M S,et al.Reactive unbalanced magnetron sputter deposition of polycrystalline TiN/NbN superlattice coatings[J].Surface and coatings technology,1993,57(1):13-18.
[25]KIM S K,LE V V,VINH P V,et al.Effect of cathode arc current and bias voltage on the mechanical properties of CrAlSiN thin films[J].Surface and coatings technology,2008,202(22-23):5400-5404.
[26]FUKUMOTO N,EZURA H,YAMAMOTO K,et al.Effects of bilayer thickness and post-deposition annealing on the mechanical and structural properties of(Ti,Cr,Al)N/(Al,Si)N multilayer coatings[J].Surface and coatings Technology,2009,203(10-11):1343-1348.
[27]WANG Y Q,NASTASI M.Handbook of modern ion beam materials analysis[M].2nd edition.Warrendale:Materials Research Society Press,2009.
[28]MAYER M.SIMNRA,a simulation program for the analysis of NRA,RBS and ERDA[C]//AIP conference proceedings.Seoul:IOP institute of physics publishing ltd,1999:541-544.
[29]KOTAI E.Computer methods for analysis and simulation of RBS and ERDA spectra[J].Nuclear instruments and methods in physics research section B:Beam interactions with materials and atoms,1994,85(1):588-596.