双脉冲HiPIMS放电特性及CrN薄膜高速率沉积
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摘要
提出了一种新型的高功率脉冲磁控溅射(HiPIMS)技术,即放电由脉宽短、电压高的引燃脉冲和脉宽长、电压低的工作脉冲2部分组成的双脉冲高功率脉冲磁控溅射技术,目的是解决传统高功率脉冲磁控溅射沉积速率低的问题。研究了引燃脉冲电压及传统高功率脉冲磁控溅射条件对Cr靶在Ar气气氛下的放电特性的影响,并制备CrN薄膜。结果表明:随着引燃脉冲电压的施加,双脉冲高功率脉冲磁控溅射Cr靶放电瞬间建立,并获得较高的峰值电流,而传统HiPIMS模式的输出是渐渐爬升的三角波电流;与传统高功率脉冲磁控溅射相比,单位功率下双脉冲高功率脉冲磁控溅射具有更高的基体电流积分以及更多的Ar~+和Cr~0数量;引燃脉冲电压为590 V时,双脉冲高功率脉冲磁控溅射单位功率下CrN薄膜沉积速率为2.52μm/(h·kW),比传统高功率脉冲磁控溅射提高近3倍。
High power impulse magnetron sputtering(HiPIMS) is of great significance for improving the quality of sputtered films because of its high ionization degree of sputtered particles and high ion fluxes. Therefore, it has been widely studied by researchers. However, the conventional HiPIMS shows a significantly low deposition rate, which greatly limits the industrial applications of HiPIMS. In this work, a novel high power impulse magnetron sputtering is proposed to enhance the low deposition rate encountered in conventional HiPIMS. The novel technology is based on dual pulses discharge mode, in which a pulsed high voltage with short duration is utilized to high-current discharge and produce initial high density plasma and a subsequent work-pulse of low voltage with long duration is employed to sustain the highcurrent discharge. Consequently the re-adsorption effect by magnetron target may be weakened. The influence of ignition pulse voltage discharge characteristics of Cr target and microstructure of CrN films were investigated. The discharge characteristics of Cr target and the structure characteristics of CrN coatings were characterized by digital oscilloscope, spectrometer, focused ion beam/electron beam dualbeam microscope and X-ray diffraction. The results show that the discharge of Cr target is ignited rapidly and the discharge current is substantially large with the ignition voltage applied to the target. In contrast,the pulse current gradually rises for the conventional HiPIMS meaning a weak discharge. Compared with the conventional HiPIMS, the dual-pulse HiPIMS produce a higher substrate current integral value and more amount of Ar+and Cr0 with the same input power. With ignition pulse voltage of 590 V, the deposition rate at unit power for CrN coating is 2.52 μm/(h · kW) for dual-pulse HiPIMS, which is nearly three times higher than that of conventional HiPIMS. With the increase of the ignition pulse voltage, the CrN films prepared by dual-pulse HiPIMS possess denser structure with smaller grain size.
High power impulse magnetron sputtering(HiPIMS) is of great significance for improving the quality of sputtered films because of its high ionization degree of sputtered particles and high ion fluxes. Therefore, it has been widely studied by researchers. However, the conventional HiPIMS shows a significantly low deposition rate, which greatly limits the industrial applications of HiPIMS. In this work, a novel high power impulse magnetron sputtering is proposed to enhance the low deposition rate encountered in conventional HiPIMS. The novel technology is based on dual pulses discharge mode, in which a pulsed high voltage with short duration is utilized to high-current discharge and produce initial high density plasma and a subsequent work-pulse of low voltage with long duration is employed to sustain the highcurrent discharge. Consequently the re-adsorption effect by magnetron target may be weakened. The influence of ignition pulse voltage discharge characteristics of Cr target and microstructure of CrN films were investigated. The discharge characteristics of Cr target and the structure characteristics of CrN coatings were characterized by digital oscilloscope, spectrometer, focused ion beam/electron beam dualbeam microscope and X-ray diffraction. The results show that the discharge of Cr target is ignited rapidly and the discharge current is substantially large with the ignition voltage applied to the target. In contrast,the pulse current gradually rises for the conventional HiPIMS meaning a weak discharge. Compared with the conventional HiPIMS, the dual-pulse HiPIMS produce a higher substrate current integral value and more amount of Ar+and Cr0 with the same input power. With ignition pulse voltage of 590 V, the deposition rate at unit power for CrN coating is 2.52 μm/(h · kW) for dual-pulse HiPIMS, which is nearly three times higher than that of conventional HiPIMS. With the increase of the ignition pulse voltage, the CrN films prepared by dual-pulse HiPIMS possess denser structure with smaller grain size.
引文
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[22]Konstantinidis S,Dauchot J P,Ganciu M,et al.Transport of ion‐ized metal atoms in high-power pulsed magnetron discharges as‐sisted by inductively coupled plasma[J].Appl.Phys.Lett.,2006,88:021501
[23]Tiron V,Velicu I L,Mih?il?I,et al.Deposition rate enhancement in HiPIMS through the control of magnetic field and pulse configu‐ration[J].Surf.Coat.Technol.,2018,337:484
[24]Konstantinidis S,Dauchot J P,Ganciu M,et al.Influence of pulse duration on the plasma characteristics in high-power pulsed mag‐netron discharges[J].J.Appl.Phys.,2006,99:013307
[25]Li C W,Tian X B,Gong C Z,et al.The improvement of high pow‐er impulse magnetron sputtering performance by an external unbal‐anced magnetic field[J].Vacuum,2016,133:98
[26]Oliveira J C,Fernandes F,Serra R,et al.On the role of the energet‐ic species in TiN thin film growth by reactive deep oscillation mag‐netron sputtering in Ar/N2[J].Thin Solid Films,2018,645:253
[27]Guimaraes M C R,de Castilho B C N M,de Souza Nossa T,et al.On the effect of substrate oscillation on CrN coatings deposited by HiPIMS and dcMS[J].Surf.Coat.Technol.,2018,340:112
[28]Wang Z Y,Xu S,Zhang D,et al.Influence of N2flow rate on struc‐tures and mechanical properties of TiSiN coatings prepared by HIPIMS method[J].Acta Metall.Sin.,2014,50:540(王振玉,徐胜,张栋等.N2流量对HIPIMS制备TiSiN涂层结构和力学性能的影响[J].金属学报,2014,50:540)
[29]Ferreira F,Serra R,Cavaleiro A,et al.Additional control of bom‐bardment by deep oscillation magnetron sputtering:Effect on the microstructure and topography of Cr thin films[J].Thin Solid Films,2016,619:250
[30]Lin J,Sproul W D,Moore J J,et al.Effect of negative substrate bi‐as voltage on the structure and properties of CrN films deposited by modulated pulsed power(MPP)magnetron sputtering[J].J.Phys.,2011,44D:425305
[31]Yang C,Jiang B L,Feng L,et al.Effect of discharge characteris‐tics of target on ionization and deposition of deposited particles[J].Acta Metall.Sin.,2015,51:1523(杨超,蒋百灵,冯林等.靶面放电特性对沉积粒子离化率及沉积行为的影响[J].金属学报,2015,51:1523)
[32]Kong Y,Ma Y H,Li Y J,et al.Microstructure and surface proper‐ties of TiCN films using cathodic arc deposition enhanced by addi‐tional electric field[J].Rare Met.Mater.Eng.,2017,46:1026(孔营,马英鹤,李永健等.电场增强的阴极弧放电TiCN薄膜结构及性能研究[J].稀有金属材料与工程,2017,46:1026)
[33]Burton A W,Ong K,Rea T,et al.On the estimation of average crystallite size of zeolites from the Scherrer equation:A critical evaluation of its application to zeolites with one-dimensional pore systems[J].Microporous Mesoporous Mater.,2009,117:75
[34]Ibrahim K,Rahman M M,Zhao X L,et al.Annealing effects on microstructural,optical,and mechanical properties of sputtered CrN thin film coatings:Experimental studies and finite element modeling[J].J.Alloys Compd.,2018,750:451
[35]Elmkhah H,Zhang T F,Abdollah-Zadeh A,et al.Surface charac‐teristics for the Ti-Al-N coatings deposited by high power impulse magnetron sputtering technique at the different bias voltages[J].J.Alloys Compd.,2016,688:820
[36]Ganesan R,Akhavan B,Dong X,et al.External magnetic field in‐creases both plasma generation and deposition rate in HiPIMS[J].Surf.Coat.Technol.,2018,352:671
[2]Liu G,Yang Y Q,Jin N,et al.The structural characterizations of Ti-17 alloy films prepared by magnetron sputtering[J].Appl.Surf.Sci.,2018,427:774
[3]Chen L,Chang K K,Du Y,et al.A comparative research on mag‐netron sputtering and arc evaporation deposition of Ti-Al-N coat‐ings[J].Thin Solid Films,2011,519:3762
[4]Sarakinos K,Alami J,Konstantinidis S.High power pulsed magne‐tron sputtering:A review on scientific and engineering state of the art[J].Surf.Coat.Technol.,2010,204:1661
[5]Odivanova A N,Podkovyrov V G,Sochugov N S,et al.Study of the plasma parameters in a high-current pulsed magnetron sputter‐ing system[J].Plasma Phys.Rep.,2011,37:239
[6]Stranak V,Cada M,Hubicka Z,et al.Time-resolved investigation of dual high power impulse magnetron sputtering with closed mag‐netic field during deposition of Ti-Cu thin films[J].J.Appl.Phys.,2010,108:043305
[7]Kouznetsov V,Macák K,Schneider J M,et al.A novel pulsed mag‐netron sputter technique utilizing very high target power densities[J].Surf.Coat.Technol.,1999,122:290
[8]Lin J L,Moore J J,Sproul W D,et al.The structure and properties of chromium nitride coatings deposited using dc,pulsed dc and modulated pulse power magnetron sputtering[J].Surf.Coat.Tech‐nol.,2010,204:2230
[9]Aiempanakit M,Kubart T,Larsson P,et al.Hysteresis and process stability in reactive high power impulse magnetron sputtering of metal oxides[J].Thin Solid Films,2011,519:7779
[10]Li C W,Tian X B.Novel high power impulse magnetron sputter‐ing enhanced by an auxiliary electrical field[J].Rev.Sci.Instrum.,2016,87:083507
[11]Anders A.Deposition rates of high power impulse magnetron sput‐tering:Physics and economics[J].J.Vac.Sci.Technol.,2010,28A:783
[12]Brenning N,Huo C,Lundin D,et al.Understanding deposition rate loss in high power impulse magnetron sputtering:I.Ionizationdriven electric fields[J].Plasma Sources Sci.Technol.,2012,21:025005
[13]Paulitsch J,Schenkel M,Schintlmeister A,et al.Low friction CrN/TiN multilayer coatings prepared by a hybrid high power impulse magnetron sputtering/DC magnetron sputtering deposition tech‐nique[J].Thin Solid Films,2010,518:5553
[14]Luo Q,Yang S,Cooke K E.Hybrid HIPIMS and DC magnetron sputtering deposition of TiN coatings:Deposition rate,structure and tribological properties[J].Surf.Coat.Technol.,2013,236:13
[15]Stranak V,Drache S,Bogdanowicz R,et al.Effect of midfrequency discharge assistance on dual-high power impulse magne‐tron sputtering[J].Surf.Coat.Technol.,2012,206:2801
[16]Lu C Y,Diyatmika W,Lou B S,et al.Influences of target poison‐ing on the mechanical properties of TiCrBN thin films grown by a superimposed high power impulse and medium-frequency magne‐tron sputtering[J].Surf.Coat.Technol.,2017,332:86
[17]Wu Z Z,Tian X B,Pan F,et al.High power pulsed magnetron sputtering discharge behavior of various target materials[J].Acta Metall.Sin.,2014,50:1279(吴忠振,田修波,潘锋等.不同靶材料的高功率脉冲磁控溅射放电行为[J].金属学报,2014,50:1279)
[18]Anders A,Andersson J,Ehiasarian A.High power impulse magne‐tron sputtering:Current-voltage-time characteristics indicate the onset of sustained self-sputtering[J].J.Appl.Phys.,2007,102:113303
[19]Wu Z Z,Tian X B,Li C W,et al.Phasic discharge characteristics in high power pulsed magnetron sputtering[J].Acta Phys.Sin.,2014,63:175201(吴忠振,田修波,李春伟等.高功率脉冲磁控溅射的阶段性放电特征[J].物理学报,2014,63:175201)
[20]Li X C,Ke P L,Liu X C,et al.Discharge characteristics of Ti and film preparation using hybrid high power impulse magnetron sput‐tering[J].Acta Metall.Sin.,2014,50:879(李小婵,柯培玲,刘新才等.复合高功率脉冲磁控溅射Ti的放电特性及薄膜制备[J].金属学报,2014,50:879)
[21]Lin J L,Moore J J,Sproul W D,et al.Modulated pulse power sput‐tered chromium coatings[J].Thin Solid Films,2009,518:1566
[22]Konstantinidis S,Dauchot J P,Ganciu M,et al.Transport of ion‐ized metal atoms in high-power pulsed magnetron discharges as‐sisted by inductively coupled plasma[J].Appl.Phys.Lett.,2006,88:021501
[23]Tiron V,Velicu I L,Mih?il?I,et al.Deposition rate enhancement in HiPIMS through the control of magnetic field and pulse configu‐ration[J].Surf.Coat.Technol.,2018,337:484
[24]Konstantinidis S,Dauchot J P,Ganciu M,et al.Influence of pulse duration on the plasma characteristics in high-power pulsed mag‐netron discharges[J].J.Appl.Phys.,2006,99:013307
[25]Li C W,Tian X B,Gong C Z,et al.The improvement of high pow‐er impulse magnetron sputtering performance by an external unbal‐anced magnetic field[J].Vacuum,2016,133:98
[26]Oliveira J C,Fernandes F,Serra R,et al.On the role of the energet‐ic species in TiN thin film growth by reactive deep oscillation mag‐netron sputtering in Ar/N2[J].Thin Solid Films,2018,645:253
[27]Guimaraes M C R,de Castilho B C N M,de Souza Nossa T,et al.On the effect of substrate oscillation on CrN coatings deposited by HiPIMS and dcMS[J].Surf.Coat.Technol.,2018,340:112
[28]Wang Z Y,Xu S,Zhang D,et al.Influence of N2flow rate on struc‐tures and mechanical properties of TiSiN coatings prepared by HIPIMS method[J].Acta Metall.Sin.,2014,50:540(王振玉,徐胜,张栋等.N2流量对HIPIMS制备TiSiN涂层结构和力学性能的影响[J].金属学报,2014,50:540)
[29]Ferreira F,Serra R,Cavaleiro A,et al.Additional control of bom‐bardment by deep oscillation magnetron sputtering:Effect on the microstructure and topography of Cr thin films[J].Thin Solid Films,2016,619:250
[30]Lin J,Sproul W D,Moore J J,et al.Effect of negative substrate bi‐as voltage on the structure and properties of CrN films deposited by modulated pulsed power(MPP)magnetron sputtering[J].J.Phys.,2011,44D:425305
[31]Yang C,Jiang B L,Feng L,et al.Effect of discharge characteris‐tics of target on ionization and deposition of deposited particles[J].Acta Metall.Sin.,2015,51:1523(杨超,蒋百灵,冯林等.靶面放电特性对沉积粒子离化率及沉积行为的影响[J].金属学报,2015,51:1523)
[32]Kong Y,Ma Y H,Li Y J,et al.Microstructure and surface proper‐ties of TiCN films using cathodic arc deposition enhanced by addi‐tional electric field[J].Rare Met.Mater.Eng.,2017,46:1026(孔营,马英鹤,李永健等.电场增强的阴极弧放电TiCN薄膜结构及性能研究[J].稀有金属材料与工程,2017,46:1026)
[33]Burton A W,Ong K,Rea T,et al.On the estimation of average crystallite size of zeolites from the Scherrer equation:A critical evaluation of its application to zeolites with one-dimensional pore systems[J].Microporous Mesoporous Mater.,2009,117:75
[34]Ibrahim K,Rahman M M,Zhao X L,et al.Annealing effects on microstructural,optical,and mechanical properties of sputtered CrN thin film coatings:Experimental studies and finite element modeling[J].J.Alloys Compd.,2018,750:451
[35]Elmkhah H,Zhang T F,Abdollah-Zadeh A,et al.Surface charac‐teristics for the Ti-Al-N coatings deposited by high power impulse magnetron sputtering technique at the different bias voltages[J].J.Alloys Compd.,2016,688:820
[36]Ganesan R,Akhavan B,Dong X,et al.External magnetic field in‐creases both plasma generation and deposition rate in HiPIMS[J].Surf.Coat.Technol.,2018,352:671