Eur. Phys. J. Appl. Phys. 42, 145151 (2008) DOI: 10.

1051/epjap:2008052

THE EUROPEAN PHYSICAL JOURNAL

APPLIED PHYSICS

Deposition of titanium nitride on AISI-304 in a plasma focus environment

S. Zeb1 , A. Qayyum2, M. Shaq1 , and M. Zakaullah1 , a
1 2

Department of Physics, Quaid-i-Azam University, 45320 Islamabad, Pakistan National Tokamak Fusion Program 3329, Islamabad, Pakistan Received: 9 December 2006 / Received in nal form: 11 December 2007 / Accepted: 23 January 2008 Published online: 29 April 2008 c EDP Sciences Abstract. Polycrystalline, smooth, and hard thin lms of TiN are successfully deposited on AISI-304 substrates using a 1.5 kJ Mather-type dense plasma focus device charged at 18 kV. The purpose of this study is to investigate the structural and mechanical properties of the TiN thin lms in terms of ion dose and substrate position to establish the optimum deposition conditions. The lms are analyzed using XRD, SEM, electron microprobe and micro-hardness testing. XRD conrms the deposition of a polycrystalline TiN thin lm together with the emergence of an iron chromium nickel phase. The surface hardness-in comparison to the unexposed substrate-is found to increase up to 250% when a lm is deposited using 30 focus shots at an axial distance of 6 cm. SEM micrographs show that the quality of the lm is improved with an increasing number of focus shots. The constituent elements of the lm are also conrmed by electron microprobe. PACS. 77.84.Bw Elements, oxides, nitrides, borides, carbides, chalcogenides, etc. 81.40.Cd Solid solution hardening, precipitation hardening, and dispersion hardening; aging 81.40.Ef Cold working, work hardening; annealing, post-deformation annealing, quenching, tempering recovery, and crystallization 68.37.Hk Scanning electron microscopy (SEM) (including EBIC)

1 Introduction
Titanium nitride lms are extensively used in numerous industrial areas owing to their superior mechanical properties such as high abrasion resistance, low friction coecient, high temperature stability and high hardness. The mechanical properties of TiN lm are strongly related to its preferred orientation [1,2]. Furthermore, it has been reported that TiN lms with a (111) preferred orientation possess the highest hardness [3,4]. During the physical vapour deposition of a thin lm, the packing density and preferred orientation of the lm normally changes with the increasing lm thickness. Therefore, lm thickness is an important parameter that aects the preferred orientation and eventually the hardness of the coating. In order to prolong service life, a TiN coating is usually chosen as a protective layer for many kinds of metal surfaces. A coating of TiN on stainless steel not only improves the corrosion resistance but also the surface hardness. A variety of technologies have been employed to deposit TiN, such as chemical vapor deposition [5], sputtering deposition [6], arc evaporation [7] and pulsed laser deposition [8]. Mukherjee et al. [9] studied TiN and Ti1x Alx N coatings deposited on Al substrates using the plasma immersion ion implantation and ltered Ti and Ti0.5 Al0.5 caa

thodic arc deposition techniques in a nitrogen environment. Shimada et al. [10] deposited TiN lms at low temperatures of 300600 C on various substrates (Silicon wafers, silica glass, and stainless steel) by injecting a titanium tetraethoxide solution at a rate of 0.050.2 ml min1 into a N2 plasma. They reported that lower feed rates of titanium tetraethoxide solution and higher N2 ow rates are eective in producing TiN lms containing ne particles with reduced O and C impurity contents. Xin-Mei et al. [11] deposited nanocrystalline Ti(Cx N1x ) lms on titanium by plasma electrolytic carbonitriding at 600 V in an electrolytic solution containing triethanolamine and formamide using a pulsed power supply. Their results showed that the lms are porous and composed of Ti(Cx N1x ), without any apparent discontinuity at the interfaces with the titanium substrate. The dense plasma focus (DPF) a highly energetic ion source has been used to eect ion-induced phase changes of dierent materials [1215]. Recently, the DPF was used to deposit AlN as an inter-layer on steel for diamond growth [16], to deposit DLC lms on silicon [17], to deposit titanium carbide lms on AISI-304 [18], to deposit titanium nitride lms (TiN) on AISI-304 [19], to deposit lead zirconate titanate (PZT) thin lms on glass, silicon and indium tin oxide (ITO) coated glass substrates [20], and for many other applications. Rawat et al. [19] reported

e-mail: mzakaullah@qau.edu.pk

Article published by EDP Sciences

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Fig. 1. Schematic of the dense plasma focus device used for the deposition of TiN on AISI-304.

the rst plasma focus assisted deposition of TiN lm on AISI-304 using a 30 F capacitor bank charged at 14 kV (2.9 kJ). They exposed the samples at axial positions of 7 cm and 10 cm away from the anode tip, and at dierent angular positions, denoted as centre, o-centre and outermost. The degree of crystallinity was improved with an increasing number of focus shots and was reduced for higher angular positions. Based on the SEM micrographs, it was concluded that the grain size progressively increased with number of focus shots. To optimize the DPF for various applications, it is important to repeat previous deposition experiments using dierent discharge parameters such as charging voltage, discharge current, and energy, and to thus verify the reproducibility of results using dierent reactors. In this work, TiN lms are deposited employing a 9 F capacitor bank charged at 18 kV. The charging voltage is thus slightly higher than that used by Rawat et al. [19] in performing the same experiments but the discharge energy is half. X-ray diraction (XRD) and scanning electron microscopy (SEM)-along with electron microprobe and micro-hardness testing- are used to explore the properties of deposited lms as a function of ion dose and substrate position.

2 Experimental
A schematic of the DPF device [21,22] used for the deposition of the TiN thin lms on AISI-304 is shown in Figure 1. It comprises a cylindrical coaxial plasma gun, closed at one end (with a Pyrex insulator between the electrodes) and open at the other end. A solid titanium

tapered anode of 110 mm length surrounded by six copper rods serves as a coaxial plasma gun. A rotary vane pump is used for the evacuation of the chamber to a base pressure of 102 mbar before the working gas is admitted. The DPF system is operated at an optimum lling gas pressure of 0.75 mbar during the deposition process, once good focusing has been achieved. The focusing eciency of the plasma focus is monitored by using a high voltage probe and a Rogowski coil. A high intensity spike in the voltage probe signal and a steep current dip in the current coil signal indicate a good focusing. Based on the high voltage probe and the Rogowski coil signals, the working gas pressure is optimized, and then the samples are exposed to focus shots at dierent positions. To transfer the energy stored in 9 F capacitor bank charged at 18 kV to the focus system, a eld distortion type spark gap is used. As the capacitor is discharged, a voltage appears across the electrodes, which initiates the development of the current sheath across the insulator sleeve. This current sheath is axially accelerated along the coaxial electrodes to the top of anode by the J B force. At the end of the anode, it undergoes a radial collapse, forming an extremely hot and dense plasma column, which is disrupted as a result of the growth of instabilities. The disruption of the plasma column during the radial phase induces an intense electric eld, which accelerates the ions and electrons in opposite directions with very high velocities. During the evolution of a macroscopic m = 0 instability, the ions are accelerated towards the top of the chamber in a conical fashion and with energies ranging from tens of keV to few MeV [23,24]. Relativistic electrons cause the ablation of anode material, and ablated active species such as ions, radicals and atoms move down the anode axis and hit the substrate. It has been reported that in a single focus shot,

S. Zeb: Deposition of titanium nitride on AISI-304

6 5 4 Voltage (volts) 3 2 1 0 3000 3250 3500 3750 4000 4250 4500
X-rays Ions

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Time (ns)

Fig. 2. Typical nitrogen ion beam signal as recorded by the GaAs detector.

Fig. 3. Photograph of nitrogen ion induced tracks on the CR39 solid-state nuclear track detector.

ions and electrons are emitted in multiple pulses, with a period of a few to tens of nanoseconds [25]. Therefore, the nitrogen ions, which reach the substrate rst, clean and heat the substrate surface prior to deposition. Titanium ions then join with the next nitrogen ion pulse (still within the same focus shot) and react to form TiN in the gas-phase and also upon reaching the substrate surface. In the next focus shot, the energetic nitrogen ions also cause the nitriding of the un-reacted titanium atoms in the lm thus increasing the TiN content in the lm. To measure the energy of the ion beam emitted from the focus region, a photoconductive GaAs detector masked with a pinhole of 50 m diameter is used at a distance of 8 cm in front of the anode tip. The detector is biased at a voltage of 300 V and the ion beam induced current creates a voltage across the load, which is recorded by a Gould 4074A four-channel digital storage oscilloscope. Figure 2 shows a typical ion beam signal recorded by the oscilloscope at an optimum discharge pressure. The rst peak in the signal corresponds to X-rays detection whereas the second peak in the signal corresponds to the ion beam emission detection. The energies of the ion beams are estimated from the signal by using the time of ight technique, and they range between 20300 keV. The ion ux is estimated by placing a CR-39 solid-state nuclear track detector (SSNTD) at a distance of 8 cm from the anode tip. Figure 3 shows that over the surface of the CR-39 detector, the spatial distribution of the ion induced tracks is almost uniform with a track density of about 6 104 tracks/mm2 . However, in another experiment the angular variation of ion ux with respect to the anode axis was studied by applying CR-39 detectors at angles of 4 and 8 at a xed axial distance from the anode tip of 20 cm. The track density was found to vary from 1.25 104 to 1.15 104 tracks/mm2 for angular positions of 4 and 8 [26]. Prior to the deposition of TiN thin lms on AISI-304, the samples are mechanically polished to a mirror nish using a Metkon GRIPO 2V polishing machine, and are

washed in methanol. The samples are then mounted on a sample holder at axial distances of 6, 8 and 10 cm at 4 from the anode axis. For the 8 cm axial distance position, there is an additional holder for samples at an angular position of 8 from the anode axis. The samples placed at these axial and angular positions are exposed to 10, 20 and 30 focus shots during the deposition of TiN lms. X-ray diraction (XRD), Vickers micro hardness testing and an electron microprobe attached to the SEM are employed to characterize the TiN thin lms for their surface properties.

3 Results and discussion

The samples of TiN thin lms deposited on AISI-304 are characterized using an X Pert MPD theta-theta X-Ray diractometer (XRD) operated at 40 kV, which uses a CuK ( = 1.544 A ) radiation source. The XRD patterns for the substrates deposited at dierent axial and angular positions are shown in Figure 4. The XRD spectra show that the deposited lms are polycrystalline and contain diraction peaks corresponding to the (111), (200) and (220) plane reections of TiN at 36 , 43 and 74 angles, respectively. These patterns conrm the successful deposition of polycrystalline TiN lms on AISI-304 substrates. Another interesting feature is noted in the XRD patterns for samples deposited at an axial position of 6 cm and at 4 (Fig. 4a). For dierent numbers of focus shots, additional diraction peaks emerge corresponding to an iron chromium nickel phase (Cr0.19 Fe0.70 Ni0.11 ) at 2 44.5 and 2 65 . These additional diraction peaks were also present in the XRD spectra reported by Rawat et al. [19]. This fact demonstrates the similarity and reproducibility of the results regarding the deposition of TiN lms by two dierent reactors using dierent energies. This additional phase is also seen in the samples at an axial position of 8 cm and at 4 (Fig. 4b) for all numbers of shots but at

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TiN Iron Chromium Nickel Stainless steel AISI 304

(6cm,4 )

(10cm,4 )

iN Iron Chromium Nickel Stainless steel- AISI 304

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Intensity (a. u.)

30 shots

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40 50 60 70 80

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30

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30

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50

60

70

80

(8cm,4 )

TiN Iron Chromium Nickel Stainless steel- AISI 304

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TiN Iron Chromium Nickel Stainless steel- AISI 304

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Intensity (a.u.)

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20 shots

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Fig. 4. XRD patterns of the lms deposited at distances of 6, 8 and 10 cm from the anode tip, and using 10, 20 and 30 focus shots.

the 8 position (Fig. 4d), it is only observed after 30 focus shots. For the sample position at 10 cm and 4 , this new phase peak also arises only after 30 focus deposition shots. These results may be due to the fact that at lower angular and axial position (6 cm, 4 ), the intensity of the ion ux is sucient to cause stoichiometric changes on the substrate surface and thus to form a new iron chromium nickel phase, which is not achievable at higher axial and angular position. Thus, the higher energy ion ux plays an important role in the formation of this new phase [19]. The careful examination of the XRD spectra (Fig. 4a) validates the role of the numbers of focus shots (ion dose) in the growth process of TiN lm. At an axial position of 6 cm the peak heights of TiN are prominent and distinct. It should be also noted here that the TiN diraction peak intensities for an axial distance of 10 cm are reduced in comparison to those for the 8 cm position. This fact suggests that the crystallinity of the TiN decreases with the increasing axial distance from the anode tip. This decrease in crystallinity may be attributed to the substantial reduction in high energy ux of nitrogen ions (which

force the TiN to go into a crystalline phase) at the more distant axial positions. Based on these results, it may be concluded that the number of focus shots (ion dose) and the substrate distance from the anode tip are the main factors inuencing the quality of the resulting TiN thin lm. Moreover, the XRD patterns of the treated samples show a slight up shift in the peak positions, compared to the corresponding original peak positions. This upwards displacement of diraction peaks to the higher side may be attributed to uniform compressive stresses induced by the contraction of the surface layer during the fast cooling down and condensation process after the fast heating by ion irradiation [27]. A Wilson Wolpert 401 MVA Vickers micro hardness tester is used to measure the surface hardness of the deposited samples positioned at distances of 6, 8 and 10 cm from the anode tip for dierent numbers of focus shots (10, 20 and 30 shots). The variation in the micro hardness of the TiN samples deposited on AISI-304 samples is shown in the Figure 5 as a function of indentation depth (m). The load is applied for a time interval of 5 seconds and the

S. Zeb: Deposition of titanium nitride on AISI-304

500 450 400
400

149

Hardness (HV)

Hardness (HV)

350 300 250 200

0 Position (4 , 6 cm) Un-Treated 10 Shots 20 Shots 30 Shots

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200

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0 2 4 6 8 10

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Indent depth (m)

Indent depth( m )

Fig. 5. Micro hardness measured as a function of indentation depth (m). The samples are deposited at distances of 6, 8 and 10 cm from the anode tip, and using 10, 20 and 30 shots.

resistance oered by the samples to deformation caused by indentation is presented in Vickers units (HV). It can be readily observed that the surface hardness depends on the number of focus shots and also on the axial and angular positions. For 30 focus shots at distances of 6, 8 and 10 cm, the hardness values are found to be 475 HV, 361 HV and 282 HV respectively. The hardness values tend to decrease when the samples are displaced axially from 6 cm to 10 cm from the anode tip. This decrease in hardness with increasing axial distance from the anode tip may be attributed to the reduced ion ux at higher axial position and, eventually less nitriding. The exposure of samples to a higher number of focus shots (1030 shots) improves the nitriding and consequently the surface hardness-due to an accumulative ion dose. At same axial distance of 8 cm, the hardness value is measured as 361 HV at 4 and 301 HV at 8 angular positions. The maximum increase in hardness is found to be a factor of 2.5 for 30 focus shots and a sample distance of 6 cm from the anode tip.

The hardness value progressively decreases with increasing load and eventually attains a value close to that of an untreated substrate. This decline of the curve means that the hardness value is sensitive to the imposed load and decreases from the surface towards the core, thus showing that the formation of a TiN lm on the surface of the substrate is responsible for the high hardness. The TiN lm formed with fewer focus shots contains un-reacted titanium species in a nitrogen environment, as is apparent from EDX analysis. An increasing number of focus shots increases the nitriding of the samples due to the interaction of nitrogen ions with un-reacted titanium species in the lm and consequently densifying the existing TiN lm. For a single focus shot, the rst pulse of nitrogen ions rst reach the substrate surface and cause cleaning and heating of the substrate prior to deposition. In the second pulse of same focus shot, both ablated titanium vapours as well as nitrogen reach the substrate, interact, and form a TiN lm on the substrate. It has been found

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Fig. 6. SEM micrographs of AISI-304, (a) before deposition (b) after sample deposition with 10 shots, (c) 20 shots, and (d) 30 shots placed at a distance of 8 cm.

that nitriding improves the hardness, which attains maximum values for 30 focus shots at axial position of 6 cm corresponding to a high titanium nitride (TiN) content. A JEOL JSM Scanning Electron Microscope (SEM) along with EDX attachment (INCA 200; Oxford Instr. UK) was used to investigate the surface morphologies and the elemental composition of the samples exposed to different numbers of focus shots (10, 20 and 30 shots). SEM micrographs presented in Figure 6 show the surface morphologies of unexposed samples (Fig. 6a) and the samples to dierent numbers of focus shots. The samples were placed at a distance of 8 cm from the anode tip, and are shown at a magnication of 5500. The untreated substrate surface appears non uniform, and shows the trenches, asperities and voids which result from polishing the samples. On the other hand, the sample treated for 10 shots shows a complete restructuring of the surface with an emergence of furrows and crests due to the sputtering and ablation caused by energetic nitrogen ions during the deposition of the titanium nitride lm. The surface of the sample treated for 20 shots appears undulating, with pits showing the redistribution and densifying of the existing lm by the successive ion beam pulses, as well as, possibly the results of sputtering. However, microcracks are observed on the sample surface which has been

treated for 30 focus shots. These may originate from the contraction of the surface layer during the fast cool-down process, thus resulting in a stressed lm. The SEM micrographs also demonstrate that the lms are densied with increasing number of focus shots. The EDX results of the lms deposited an axial position at 8 cm, and for dierent numbers of focus shots (10, 20 and 30 shots) are summarized in Table 1. The results show that the titanium and nitrogen content in the TiN lm is increased with an increasing number of shots (10 to 30 shots), suggesting the increased nitriding of samples. For the treated samples at 8 cm, the maximum titanium and nitrogen contents are found to be 26.5 at. % and 35.9 at. % measured after 30 focus shots. The results of TiN crystalline thin lms formed on AISI 304 are compared to those of Rawat et al. [19]. They used a 2.9 kJ DPF system and observed crystalline TiN thin lms. In the present work, we used a 1.5 kJ DPF system and found that good quality crystalline lms are formed at half the value of discharge energy. Rawat et al. [19] reported that the degree of crystallinity increases with an increasing number of focus shots and decreases from centre to outer angular positions. Identically, in our case, the degree of crystallinity also increases with number of focus shots, and depends on the distance from

S. Zeb: Deposition of titanium nitride on AISI-304 Table 1. Titanium and nitrogen content of the TiN lms deposited on AISI 304 stainless steel substrates as determined by EDX. Substrates were placed at 8 cm from the anode tip and were exposed to a varying number of focus shots. Number of Titanium concentration Nitrogen concentration focus shots Atomic % Weight % Atomic % Weight % 10 20.8 24.0 21.0 7.1 20 24.2 29.2 26.9 11.7 30 26.5 40.5 35.9 16.1

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This work was partially supported by the Quaid-i-Azam University Research Fund and the Higher Education Commission (HEC) Research Project No. 20-743 (R&D) for Plasma Physics. We acknowledge Dr. Riaz Khan and Mr. Khalid Shah of Centralized Resource Laboratory, Peshawar University, for carrying out the SEM and EDX analysis. Shaista Zeb acknowledges the nancial support of HEC for her doctoral studies.

References
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anode axis. Rawat et al. [19] measured the hardness of selected samples positioned at 7 cm (centre and o centre) deposited with 10 and 20 shots. They reported that the hardness of the TiN lms increases from 1114 GP with an increase of 1020 focus deposition shots. For 30 focus shots, they observed an increase in the hardness of the sample at the o centre position at the same distance. It was qualitatively discussed that the hardness value increases due to change in the surface morphology such as grain size and bonding. From SEM micrographs, it was reported that bigger size grains are formed when the number of focus shots are increased. In comparison to their work, we have measured the hardness quantitatively for samples positioned at 6, 8 and 10 cm and with dierent numbers of focus shots (1030). From EDX results, it is clear that when the number of focus shots increases, the nitrogen and titanium contents are increased. As shown by the increase in nitrogen content, more nitriding of the samples takes place yielding the higher hardness. Finally the TiN thin-lm samples were baked at 300 C for three hours in a furnace. There was no appreciable change in the hardness of the samples. For the sample at an axial distance of 6 cm, the hardness even decreased after heat treatment. For an axial position of 10 cm and an angular position of 8 , there is a slight increase of about 15% in the hardness of the samples. At an axial position of 8 cm, the hardness increases up to 25% compared to that of the unheated sample.

4 Conclusions
The XRD pattern of the deposited samples conrms the formation of polycrystalline TiN thin lms along with the emergence of an iron chromium nickel phase. The maximum hardness is found to be 474 HV at a distance of 8 cm from the anode tip and with 30 focus shots. In general, closer angular positions yield higher surface hardness and more Ti and N content in the lm. For smaller distances from the anode tip, the lms are more crystalline and are harder. SEM micrographs reveal that microcracks are present on the sample surface when deposited by 30 focus shots, which may be due to the contraction of the surface layer during the fast cool-down process creating stress in the lm. EDX results show that the content of titanium and nitrogen in the lm increases with an increasing number of focus shots.