Characterization of advanced coating architectures deposited by an arc-HiPIMS hybrid process

Accepted Manuscript Characterization of advanced coating architectures deposited by an arc-HiPIMS hybrid process

J. Vetter, K. Kubota, M. Isaka, J. Mueller, T. Krienke, H. Rudigier PII: DOI: Reference:

S0257-8972(18)30560-7 doi:10.1016/j.surfcoat.2018.05.075 SCT 23450

To appear in:

Surface & Coatings Technology

Received date: Revised date: Accepted date:

16 January 2018 29 May 2018 30 May 2018

Please cite this article as: J. Vetter, K. Kubota, M. Isaka, J. Mueller, T. Krienke, H. Rudigier , Characterization of advanced coating architectures deposited by an arc-HiPIMS hybrid process. Sct (2017), doi:10.1016/j.surfcoat.2018.05.075

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ACCEPTED MANUSCRIPT Characterization of advanced coating architectures deposited by an arc-HiPIMS process: Revised Version 2: 29May2018 J. Vetter, K. Kubota, M. Isaka, J. Mueller, T. Krienke, H. Rudigier

Characterization of advanced coating architectures deposited by an arc-HiPIMS hybrid process

J. Vetter1, K. Kubota2, M. Isaka2, J. Mueller1, T. Krienke1, H. Rudigier3 1 Oerlikon Balzers Coating Germany GmbH, Am Boettcherberg 30-38, 51427 Bergisch

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Gladbach, Germany

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2 Mitsubishi Hitachi Tool Engineering, 35-2, Mikami, Yasu-shi, Shiga-ken, 520-2323, Japan

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3 Oerlikon Surface Solutions Ltd Trübbach, Branch Balzers, 9477 Trübbach, Switzerland

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[email protected]

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Abstract We describe advanced coating architectures achieved by a novel combined vacuum arc evaporation/HiPIMS PVD-system which permits us to exploit the advantages of both processes. This system combines three highly ionized processes - arc evaporation, classical HiPIMS and Arc Enhanced Glow Discharge (AEGD). The process technology is

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commercially named HI3 (High Ionization Triple). The ion cleaning is based on the AEGD

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process. The tailoring of coating architectures is driven by the advantages of the individual

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techniques. Vacuum arc evaporation has limitations concerning the materials which can be evaporated, but is characterized by high process stability and high deposition rates, while

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sputter-deposition is implemented to provide a more complex composition and to achieve multilayer architectures with enhanced properties. Magnetron sputtering processes can be

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used to atomize materials which are difficult to evaporate by vacuum arc evaporation e.g. Si, SiC, WC, TiB2 and others. The high ionization of the HiPIMS process results in a dense

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coating structure even for nitride top coatings (e.g. VZrN). Both deposition methods can be

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run as individual process steps, and also in a hybrid mode. The HI3 This hybrid process opens a window to generate multilayer as well as nanomultilayers down to sub-nanometer layers.

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Functional top layers with outstanding properties can be deposited in addition. Selected advanced coating architectures are highlighted. TiB2, SiBC and VZr targets were used to

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generate individual HI3 hybrid coating architectures in combination with arc deposited AlTiN coatings. Every coating started with an AlTiN base coating, followed by a hybrid coating and a HiPIMS top coating. Also classical arc coatings using AlTi and TiSiX cathodes were deposited and investigated to work out the differences to the HI3 hybrid coatings. TEM preparations were done for each coating type and investigation of nano beam diffraction were made for the top coating deposited by pure classical HiPIMS. Structural evolutions are discussed. Keyword: Arc, sputtering; hybrid, classical HiPIMS, sub-nanometer, multilayer coatings

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1. Introduction The vacuum arc evaporation and the magnetron sputtering are the main PVD deposition methods to produce tribological and other functional coatings in industrial scale. The application of vacuum arc evaporation is the dominating PVD method for tool coatings and high performance component coatings [1, 2]. Classical DC-magnetron sputtering (DC-MS) is

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mainly used for a-C:H:Me coatings or for the deposition of interlayers for a-C.H:X coatings

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[3]. Although the DC-magnetron sputtering process often results in smoother coatings the

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number of coating systems in industrial use for wear reduction of tools is much lower than that of arc evaporation. The reasons for that are the advantages (stability, productivity, costs,

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and coating properties) of the arc evaporation process in industrial scale. Hybrid solutions combining arc evaporation with classical DC-magnetron sputtering in one PVD chamber was

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reported by several groups. First use was a sputtered coatings (e.g. Au) at the top of arc coatings for decorative purposes [4]. Later the so called arc bond sputtering (ABS) was in the

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scope of research. The arc discharge was used for ion cleaning before a sputter coating was

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deposited [5]. Later also the hybrid operation of arc evaporation and sputtering to create multilayers was investigated [6]. However the ionization of classical DC-magnetron

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sputtering is mostly dominated by the sputter gas ionization (mostly argon). The HiPIMS process generates a discharge consisting of a mixture of ionized gases (mostly

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argon) with a high ionization of the sputtered atoms [7-10].This higher ionization level of the magnetron sputtering process opens up new possibilities to tailor coating properties. The classical HiPIMS processes using short pulses have different trade names, e.g. HPPMS [11], HIPAC [1] and others, HIPAC is used by Oerlikon Balzers (High Ionized Plasma Assisted Coating). But also longer pulses are in use (e.g. MPP) [10]. An outstanding innovative method using long pulses is the s3p method developed by Oerlikon Balzers [12] and is successfully applied in industrial coaters. The common goal is to deposit droplet minimized coatings showing similar properties to arc coatings.

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The HI3 novel arc-HiPIMS hybrid process follows another innovative way [13, 14]. A brief description of the HI3 hybrid deposition process is made in the following. The HI3 deposition process combines specific features and advantages of the arc and of the HIPAC HiPIMS processes. The ion cleaning is carried out by the powerful AEGD process [15]. The arc evaporation has some limitation to evaporate materials. Mostly metals and its alloys are

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evaporated. Furthermore, it is not possible to eliminate all droplet emissions in the productive

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direct arc mode (only almost in the filtered arc mode). However, the amount of droplets is

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acceptable for most of the applications (tool, components, decoration). Different cathode materials result in different droplet emissions, e.g. VN has a much higher droplet content than

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CrN.

HIPAC HiPiMS as a sputtering process has the advantage that it is also possible to atomize

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and ionize materials which are not possible to evaporate by arc like Si, B4C and more, others materials which show a high droplet emission like Vanadium. Thus the HI3 arc-HiPIMS

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hybrid process is suitable to generate new advanced coatings like sophisticated top layers

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(oxidation- , friction- , wear reduction and more) on arc layers by HIPAC HiPIMS, doping of arc deposited layers within a layer stack by HIPAC HiPIMS, deposition of nanolayers down

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to sub-nanometer layers running arc and HIPAC HiPIMS with optimized process parameters at the same time.

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Selected advanced coating architectures are highlighted. VZr, SiBC and TiB2 targets were used to generate HI3 hybrid coating architectures in combination with arc deposited AlTiN coatings. Vanadium based coatings offers promising phases in order to enhance the tribological properties of wear protecting coatings, due to their ability to form lubricious oxides, often also referred to as Magneli phases, at elevated temperatures [16]. SiBCN was chosen as an example for an extreme oxidation protection top coating [14]. Application tests for various industrial tools were reported in references [14].TiB2 was used to demonstrate the possibility to deposit a hard wear protecting top coating [17]. Classical arc coatings using

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AlTi and TiSiX cathodes were deposited to work out the differences of the HI3 hybrid coatings. TEM preparations were done for each coating type and investigation of nano beam diffraction were made for the top coating deposited by pure classical HiPIMS. Structural evolutions are discussed. 2. Experimental details

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A METAPLAS.DOMINO S industrial coater equipped with two face to face arranged arc

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flanges and two face to face oriented magnetron sputtering sources were used to deposit the

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coatings. This configuration is showing in Fig. 1

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METAPLAS.DOMINO S

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Fig. 1: Set up of the arc sources and magnetrons for the HI3 arc-HiPIMS hybrid process in the

Magnetrons were mounted in a closed field configuration. The magnetrons were powered by a

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HiPIMS power supply with maximum current of 1000A and maximum voltage of 1000V. Cemented carbide samples were cleaned by a standard industrial cleaning line. The samples

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were loaded onto an industrial standard substrate holder on plates which allow a threefold rotation. The rotation speed of the carousel was held constant at 2 rpm. Standard industrial cemented carbide inserts were used as samples. First the samples were heated to about 500°C by radiant heating. Intense ion cleaning was done by AEGD [15]. Five different coating architectures were deposited as shown in Fig. 2.

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Fig. 2: Coatings architecture of pure arc coatings and HI3 hybrid coatings: C = arc cathode

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materials C1: Al55Ti45 (at%), C2: TiSiX, C3: Al50Ti50 (at%), Tx = magnetron target

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material, (VZr or SiBC orTiB2)

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Two different architectures were deposited by two arc flanges only. One flange was equipped with Al55Ti45 cathodes the other with TiSiX cathodes. The base coating was always AlTiN.

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The classical two layer coatings that were deposited were composed of a thick AlTiN coating

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with a TiSiXN coating on top. The TiSiX cathodes contain 18.5 at% Si and 1.5 at% Ce. The second coating was a complex multilayer. First an AlTiN base coating was deposited

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followed by a nanomultilayer generated by running of AlTiN and TiSiXN evaporators at the same time. A TiSiXN top coating was deposited onto the nanomultilayer coating. All pure arc

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coatings were deposited applying an arc current of 150 A and a negative bias of 50 V, also when deposited as bond coatings before the hybrid phases in the HI3 process. Three different HI3 hybrid coatings based on the same architectures were deposited by using two arc flanges equipped with Al50Ti50 cathodes and three different magnetron targets (Tx): VZr, SiBC and TiB2. The V was alloyed with 2.5 at% Zr. The SiBC target had a composition of 66 at% Si, 22 at% B and C 12 at% C. Both magnetrons were equipped with the same target material (Tx). The first coating step was always a pure AlTiN arc coating, followed by a hybrid phase done by a parallel running of the arc discharge and classical HiPIMS discharge

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with short pulses in the range of several 10 us. Nitrogen was introduced as the reactive gas. The average power applied to each target was lower for the ceramic bonded targets (2.5 kW for SiBC, 4 kW for TiB2) than for the metallic target (10 kW for VZr). The peak power of a pulse was 300 W/cm2 for the ceramic targets and 1000 W/cm2 for VZr. A bias voltage of 50 V was applied during the hybrid phase. The top coating was always a pure HiPIMS coating by

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operating the two targets in a classical HiPIMS mode. Nitrogen was introduced as the reactive

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gas for VZrN and SiBNC top coatings. Of course TiB2 coatings were non-reactive deposited.

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All coatings were deposited in three fold rotation. The applied bias voltages were 200 V for TiB2, 50 V for VZrN and 30 V for SiBNC top coatings deposited by HiPIMS discharge.

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The substrate current was measured by a time integral current sensing process that was optimized for a standard unpulsed direct current. The substrate current was used in the pure arc phase to

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deposit an AlTiN film at about 12 A of current. The substrate currents were slightly higher in the following hybrid process (zone 1): 12,9 A for the SiBNC based process, 13,8 A for the VZr based

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process and 13,5 A for the TiB2 process. The substrate currents of hybrid zone 2 were lower due

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to the operation of only half of the arc evaporators: 6,8 A for the SiBNC based process, 7,5 A for the VZr based process and 7,3 A for the TiB2 process. The time integral substrate current for the

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top coating deposited by HiPIMS was 0,9 A for SiBNC, 1,6 A for VZrN and 1,8 A for TiB2.

Hardness measurement was done by using a Berkovich indenter with a load of 10 mN both at

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samples prepared by 5° tilt angle and in calottes. The measurement was done choosing the areas of the single layers within the coating stack visible in the cross section. The average values are shown in the graph. TEM sample preparation was made by FIB (equipment Hitachi High-Tech Science Corporation, type: XVision200TB). The acceleration voltages were 30 kV, 15 kV, 5 kV. The TEM investigation was done by a JOEL Ltd. equipment (type mages JEM-2010F). An acceleration voltage of 200 kV was chosen.

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3. Results

The architecture of two classical arc coatings are shown to work out the specific characteristics of the arc-HiPIMS hybrid be similar to the coating architectures of HI3 coatings. Fig. 3 shows the two layer arc coating. The columns width (grain size) growths over

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the coating thickness for the AlTiN coating as shown in Fig. 3a. The grain size drops down with the coating thickness of the TiSiXN coating on top. A clear fcc structure is shown for the

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TiSiXN in Fig. 3b.

Fig. 3: TEM images of classical two layer architecture deposited by arc: AlTiN/TiSiXN

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a) overview over the total coating, b) nano beam diffraction of the top coating

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Fig. 4 shows the complex multilayer architecture consisting of a base layer (AlTiN), followed by nanomultilayer (AlTiN/TiSiXN) with aTiSiXN top coating. The multilayer structure is clearly visible in Fig. 4a.The bilayer thickness was measured to be 64 nm. Each single layer within the coating sequence has around the same thickness of 32 nm. A nano beam diffraction result of the top coating is presented in Fig. 4b. The TiSiXN coating shows more diffuse reflections than for the two layer coating. That means that the coating properties of the top coating are influenced by the coating type growing before. It seems that the column size is smaller.

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Fig. 4: Complex multilayer architecture deposited by arc AlTiN/(TiSiXN-AlTiN)n/TiSiXN

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a) overview over the total coating, b) nano beam diffraction of the top coating

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The HI3 hybrid coating architecture has some similarities to the coating architecture of the complex multilayer deposited by classical arc. In the following a TEM image of the whole

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coating and a detail TEM image of the hybrid zone 2 are presented to highlight the structure. Fig. 5a shows an overview about the total coating using the VZr magnetron target. A growth

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of the column size is visible from the AlTiN deposited at the substrate till the hybrid zone 2.

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The multilayer structure of the hybrid zone 1 can be seen also in Fig. 5a with the low magnification. The TEM image of the hybrid zone 2 at the higher magnification is shown in

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Fig. 5b. Sharp interfaces between the AlTiN and VZrN single coatings were generated. The thickness of the AlTiN coating is about 32 nm. The thickness of the VZrN is about 4 nm in

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the zone 2. A nano beam diffraction of the top coating show that the phases might be the fcc VZrN or cubic V(Zr)4N3 crystalline structure.

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Fig. 5: TEM images of HI3 the hybrid coating architecture using the classical HiPIMS

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process for VZrN and arc evaporation of AlTiN

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a) overview over the total coating, b) hybrid zone 2 with a nano beam diffraction of the top coating

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Fig. 6a shows an overview of the total HI3 hybrid coating deposited using the TiB2 magnetron target. A growth of the column size of the AlTiN and also in the hybrid zone 1 is visible. A multilayer structure cannot be seen at the magnification in the hybrid zone 1. However a grain

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refinement starts in the hybrid zone 2. The TEM image of the hybrid zone 2 at the higher

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magnification presented in Fig. 6b shows sharp interfaces between the AlTiN and TiBNx single coatings. The thickness of the AlTiN coating is about 32 nm but the thickness of the TiBNx is only about 1 nm. The nano beam diffraction of the top coating was made in two areas. The TiB2 coating directly deposited at the multilayer shows diffuse reflections, which means it is an extremely fine grained or even an amorphous coating whereas the coating on top shows a clear hexagonal TiB2 structure.

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Fig. 6: TEM images of HI3 the hybrid coating architecture using the classical HiPIMS

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process for TiB2 and arc evaporation of AlTiN

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a) overview over the total coating, b) hybrid zone 2 with a nano beam diffraction of the top coating

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Fig. 7a shows a TEM image of the whole HI3 hybrid coating deposited using the SiBC magnetron target. A slightly grain refinement starts in the hybrid zone 1. The multilayer structure is not visible in the hybrid zone 1. An extreme refinement occurs in the hybrid zone

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2. The TEM image of the hybrid zone 2 at the higher magnification presented in Fig. 7b

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shows diffuse interfaces between the AlTiN and SiBNC single coatings. The thickness of the AlTiN coating is about 32 nm. The thickness of the SiBNC can be only roughly estimated with about 1 nm because the boundaries are diffuse. The nano beam diffraction of the top coating show that the top coating is an amorphous coating.

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Fig. 7: TEM images of HI3 the hybrid coating architecture using the classical HiPIMS

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process for SiBC and arc evaporation of AlTiN

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a) overview over the total coating, b) hybrid zone 2 with a nano beam diffraction of the top coating

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Hardness measurements were performed for each of the HI3 hybrid coatings: the base AlTiN

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coating, the total hybrid coating and the top layer. The results are shown in Fig. 8. As it can be seen the coatings have different hardness gradients. A positive gradient has the TiB2-HI3

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based hybrid coating with a high hardness of the top coating of about 40 GPa. A negative hardness gradient was measured for the VZr-HI3 based hybrid coating. The hardness of the

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SiBC-coating has first an increase from the base AlTiN layer to the hybrid layer but then drops down.

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Fig. 8: Hardness measurements of the base AlTiN coating, hybrid coating and top layer of HI3 hybrid coatings.

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It should be pointed out that the coating properties of the top coatings can be tailored by the

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HiPIMS discharge parameters as shown as example for TiB2 in Fig. 9. The coating texture coefficient [001]/[002] is highest at high peak pulse densities. Both the hardness and the stress

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in the coating are increasing in parallel. The hardness can achieve values larger than 40 GPa.

Fig. 9: Hardness of TiB2 top coatings and x-ray diffraction results versus peak power density in the classical HiPIMS mode and DC sputtering

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4. Discussion

A schematic drawing of the observed different coating architectures of the multilayer structures of both the HI3 arc-HiPIMS hybrid coatings in the hybrid zone 2 and the arc coating is presented in Fig 10. In the following the differences between the coating structure

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itself and the possibilities to adjust a single layer thickness are discussed.

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Fig. 10: Schematic drawing of the multilayer structure of classical arc coating and of the

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hybrid zone 2 of HI3 arc-HiPIMS hybrid coatings

Classical arc multilayer coatings can be deposited with a high rate (1 to 2 um/h) in three fold

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rotation. The standard rotation speed of the one fold rotation with 2 rpm resulted in a bilayer

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sequence of 62 nm. Both materials had about the same growth rate during one rotation (see also Fig.1). To generate a finer nanolayer the rotation speed has to be increased, by calculation to about 60 rpm, to have around 1nm coating thickness of the single layer which is not really a practical speed for industrial systems. Another but more limited way to decrease the thickness of the single layers is to lower the arc current, but this is mostly limited by a factor two (references), however it is a way to steer the ratio between the thickness of the single layers. In conclusion there are some practical limitations to generate multilayers with

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single layers near the 1 nm range and also a variation of the thickness ratio is strongly limited if standard industrial systems are used.

Two different multilayer structures were observed for hybrid zone 2 of HI3 arc-HiPIMS hybrid coatings. Due to the significantly lower growth rate of the HiPIMS single layers a

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pronounced thickness difference to the arc single layers can be seen. This opens a window for a sub-nanometer design of at least one single layer. The multilayers have sharp interfaces for

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TiB2 and VZr targets with a thickness ratio to the arc single layer of 1:32 for TiBNx and 1:8

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for VZrN. Diffuse interfaces are visible if SiBC targets were used. The light elements might diffuse in to the AlTiN arc single layers. The multilayer generation can be seen for VZr

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targets also in the hybrid zone 1. The VZrN has a thickness of about 2 nm in hybrid zone 1.

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The thickness of the TiBNX single layers are by calculation in the sub-nanometer range, only 500 pm. The multilayer structure of hybrid zone 1 is not visible in Fig. 6a.

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More investigations have to be done. The question arises: how thick a certain sputtered

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material can be detected as an own single layer depending upon the deposition condition (e.g. temperature). It can be speculated that there will be a great difference between target with

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only light elements (SiBC) and with heavy elements (e.g. VZrN). If the thickness of the sputtered material is very low (some atomic monolayers) only a kind of a “two dimensional”

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tissue phase might be generated between the arc single layers, in extreme case also a kind of “doping” only.

The top coatings deposited by classical HiPIMS process also show specific features. It is possible to deposit different kinds of materials both in the hybrid phase and as top coatings like dense magneli phase forming vanadium-based coatings (16), amorphous oxidation protecting non-oxide ceramic coating like SiBNC (14) and wear reducing hard coatings like

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TiB2(17). It was shown that the first TiB2 layer grows almost amorphous and then in a hexagonal crystal structure.

One aspect is till now not investigated: what are the changes in the plasma condition and coating growth if the classical HiPIMS and the arc process is running in parallel in a hybrid

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phase?

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The different hardness gradients might have an influence on the tribological behavior. The TiB2-HI3 based hybrid coatings show a “classical” positive hardness gradient for wear

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protection, whereas the VZr-HI3 based hybrid coating a “classical” negative gradient useful

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for running in processes. The SiBC-HI3 based hybrid coating shows first a hardness increase, however the oxidation protective amorphous SiBNC top coating cannot be deposited with a

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higher hardness.

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5. Summary and conclusions

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1. Extreme fine nano layers can be generated due to the difference in the growth rate between arc evaporations and classical HiPIMS sputtering. Top layers with tailored properties can be

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deposited.

2. The adjustment of coating architecture and the material selection of coatings deposited in

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pure industrial standard vacuum arc coaters are limited. 3. The HI3 arc-HiPIMS hybrid coatings can be deposited in a complex architecture e.g. arc base layer, hybrid zone 1, hybrid zone 2 and top layer. More complex architectures are easy to realize.

4. The hardest top coating deposited in the of HI3 by the arc-HiPIMS hybrid process is TiB2 with around 40 GPa of hardness. 5. Hardness profiles with positive (HI3-TiB2 based hybrid coatings) or negative gradients (e.g.

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HI3-VZr based hybrid coatings) can be deposited. 6. HiPIMS discharge parameters are applied to tailor the coating, e.g. the hardness and texture of TiB2 top coating. 7. The thickness ratio of the sputtered and arc coating in the hybrid phase can be varied by the active arc growth rate and the setup of the system although the maximum growth rate of the

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sputter process is limited.

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8. Sub-nanometer layer designs of at least one single layer can be realized.

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9. One aspect of the hybrid process has to be investigated. What are the changes in the plasma discharge and coating growth if the classical HiPIMS and the arc process are in parallel

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References

[1] G. Erkens, J. Vetter, J. Mueller; A. Mohnfeld, Plasma-Assisted Surface Coating Verlag Moderne Industrie, Landsberg Germany 2011 [2] R.L. Boxman, P.L. Martin, D.M. Sanders: Handbook of vacuum arc science and

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technology, Noyes Publications, New Jersey, 1995 [3] J. Vetter, 60 years of DLC coatings: Historical highlights and technical review of cathodic

RI

arc processes to synthesize various DLC types, and their evolution for industrial applications,

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Surf. Coat. Technol. 257 (2014) 213-240

[4] M. J. Buske; H. S. Randhawa, Physical vapour deposition dual coating process, patent,

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US000005234561A, 1993

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[5] W.-D. Münz, F. J. M. Hauzer, D. Schulze and B. Buil, A new concept for physical vapour deposition coating combining the methods of arc evaporation and unbalanced-magnetron

D

sputtering, Surf. Coat. Techn. 49(1991)161-167

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[6] C.-S. Lee, K.-R. Lee, S.-H. Suh, Mechanical property optimisation of materials by nanostructuring: reduction of residual compressive stress in ta-C film, Mater. Sci. Techn. 20 (2004)1-3

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[7] Khodachenko G.V., Mozgrin D.V., Fetisov I.K. patent in russian RU2058429, 1993

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[8] U. Helmersson, M. Lattemann, J. Bohlmark, A.P. Ehiasarian, J.P. Gudmundsson, Ionized physical vapor deposition (IPVD): A review of technology and applications, Thin Solid Films, 513(2006) 1-24

[9] A. Anders, High power impulse magnetron sputtering and related discharges: Scalable plasma sources for plasma‐based ion implantation and deposition Surf. Coat. Techn. 204(2010) 2864 [10] A. Anders, Tutorial: Reactive high power impulse magnetron sputtering (R-HiPIMS), J. Appl. Phys. 121(2017)171101

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[11] K. Bobzin, T. Brögelmann, N. C. Kruppe, M. Engels, A. von Keudell, A. Hecimovic, A. Ludwig, D. Grochla,L. Banko, Fundamental study of an industrial reactive HPPMS (Cr,Al)N process, J. Appl.Phys. 122(2017) 015302 [12] https://www.oerlikon.com/balzers/baliq/s3p.php#s3p.php, 15. January 2018 [13] J. Vetter, J. Müller, G. Erkens, G.: Domino Platform: PVD coaters for Arc Evaporation

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and High Current Pulsed Magnetron Sputtering, IOP Conf. Series: Mater. Sci. Eng.

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39(2012)012004

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[14] G. Erkens, J. Vetter, J. Müller, T. Krienke, About the synthesis of next generation high oxidation resistant hard coatings by means of novel High Ionization Hybrid PVD Processing,

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Proceedings Plansee Seminar 2013, Reutte/Austria, 3-7 June, 2013,1366 [15] J. Vetter, A.J. Perry, Advances in cathodic arc technology using electrons extracted from

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the vacuum arc, Surf. Coat. Techn. 61(1993)305

[16] G. Gassner, P.H. Mayrhofer, K. Kutschej, C. Mitterer, M. Kathrein, A new low friction

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Lett. 17(2004)751

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concept for high temperatures: lubricious oxide formation on sputtered VN coatings, Tribol.

[17] Teng Fei Zhang, Bin Gan, Seong-mo Park, Qi Min Wang; Kwang Ho Kim,

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Influence of negative bias voltage and deposition temperature on microstructure and properties of superhard TiB2 coatings deposited by high power impulse magnetron sputtering,

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Surf. Coat. Techn. 253(2014)115-122

ACCEPTED MANUSCRIPT Characterization of advanced coating architectures deposited by an arc-HiPIMS process: Revised Version 2: 29May2018 J. Vetter, K. Kubota, M. Isaka, J. Mueller, T. Krienke, H. Rudigier

Highlights

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Arc-HIPIMS hybrid deposition process realized using based on a combined vacuum arc /HiPIMS in one PVD-system (commercially called HI3) Coatings have the structure: arc base layer, hybrid zone 1 and 2, plus top layer

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As sputtering targets were used VZr, TiB2 and SiBC.

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AlTi and TiSiXN targets were evaporated by arc

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TEM preparations and investigation of nano beam diffraction were done

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