Thin Solid Films 517 (2009) 18871894

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Thin Solid Films

j o u r n a l h o m e p a g e : w w w. e l s ev i e r. c o m / l o c a t e / t s f

A comparative study of CrNx coatings Synthesized by dc and pulsed dc magnetron sputtering

J. Lin a,, Z.L. Wu a,b, X.H. Zhang a,c, B. Mishra a, J.J. Moore a, W.D. Sproul d
a

Advanced Coatings and Surface Engineering Laboratory (ACSEL), Colorado School of Mines, Golden, Colorado, USA Surface Engineering Laboratory, School of Materials Science and Engineering, Dalian University of Technology, Dalian 116024, China Department of Material Science and Engineering, South East University, Nanjing 210096, China d Reactive Sputtering, INC, 2152 Goya Place, San Marcos, California, USA
b c

a r t i c l e

i n f o

a b s t r a c t
Chromium nitride (CrNx) coatings were prepared by reactively sputtering chromium metal target with various nitrogen ow rate percentages (fN2) using a closed eld unbalanced magnetron sputtering system operated in dc and middle frequency pulsed condition (100 kHz and 50% duty cycle). In this study, plasma examination proved that a large amount of ions with a wide range of ion energies (up to 65 eV and mainly from 1030 eV region) was identied in the pulsed plasma compared to the low ion ux and energy (010 eV) in a dc discharged plasma. The results showed that the phase structure of CrNx coatings was changed from nitrogen doped Cr(N) to pure -Cr2N, and to a mixture of -Cr2N and c-CrN and then to pure cCrN phases with an increase in the fN2 in both dc and pulsed conditions. However, the pulsed CrNx coatings exhibit lower N concentrations than dc CrNx coatings prepared under the same fN2, which leads to the existing of -Cr2N phase within a wide range of fN2 (3050%). In comparison with the typical large columnar structure in the dc sputtered coatings, the pulsed CrNx coatings exhibit dramatic microstructure improvements which beneted from the improved plasma density and ion bombardment from the pulsed plasma, where the super dense and nearly equi-axial structures were observed in a wide range of fN2. The microstructure improvements contributed to the enhancements in the hardness and wear resistance of pulsed CrNx coatings. In the pulsed CrNx coatings, the hardness values were above 30 GPa when the fN2 is in the range of 3040%, which is related to the formation of the -Cr2N phase. With the formation of a mixture of -Cr2N and c-CrN phases in the coatings deposited with 4050% fN2, a low COF of 0.36 and wear rate of 1.66 10 6 mm3 N 1 m 1 can be achieved. Published by Elsevier B.V.

Article history: Received 15 July 2008 Received in revised form 24 September 2008 Accepted 25 September 2008 Available online 7 October 2008 Keywords: Chromium nitride (CrN) Pulsed magnetron sputtering (PMS) Hard coatings Ion energy distribution (IED) Plasma diagnostic Wear

1. Introduction Chromium nitride (CrN) coating has attracted scientic attention for many years due to their high hardness, good wear and oxidation resistance [113]. It also exhibits superior corrosion resistance than titanium based nitride. These characteristics make CrN an excellent protective candidate in forming tools, die casting dies, and wear protection applications as a replacement for chromium electroplating. Reactive magnetron sputtering is an effective technique to synthesize CrNx coatings by sputtering metal chromium target in the nitrogen reactive atmosphere. In recent years, the pulsed magnetron sputtering (PMS) technique has been widely used for producing nonconducting materials in a near arc free process with desired adhesion [1416]. Compared to low plasma density in the conventional dc magnetron sputtering, increased ion ux with a wide ion energy distribution (up to hundreds of eV) has been well documented within the pulsed plasma in PMS [1719]. The increased ion energy and ion
Corresponding author. Tel.: +1 303 273 3178; fax: +1 303 273 3795. E-mail address: jlin@mines.edu (J. Lin). 0040-6090/$ see front matter. Published by Elsevier B.V. doi:10.1016/j.tsf.2008.09.093

ux within a pulsed plasma could have critical effects on the composition, texture, microstructure and properties of the coatings [2023]. It was also recognized that the compositions, phase structure, texture, grain size and properties of CrN coatings are strongly inuenced by the reactive nitrogen gas content, the applied substrate bias and the substrate temperature [39]. Depending on the nitrogen content, the CrN coatings may consist of Cr, -Cr2N, c-CrN and/or mixtures of these phases. It was also found that the nitrogen gas content in the sputtering atmosphere will change the discharged plasma ion energy distributions, for example, a decrease in the maximum ion energy with an increase in the reactive nitrogen gas percentage was found in pulsed closed eld magnetron sputtering of CrAlN coatings [17]. Accordingly, CrNx coatings were synthesized by dc and pulsed reactive magnetron sputtering at various nitrogen ow rate percentages in a closed eld unbalanced magnetron sputtering (CFUBMS) system. The ion energy distributions (IED) in the discharged plasma were characterized using an electrostatic quadrupole plasma mass spectrometer (EQP). Comparative studies of the compositions, microstructure, mechanical and wear resistance properties between dc and pulsed CrNx coatings were carried out using grazing incident X-ray diffraction (GIXRD), eld

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emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM), nanoindentation and microtribometry. 2. Experimental details CrNx coatings were synthesized in a CFUBMS system by sputtering a metal Cr target (100 mm 280 mm) in a gas mixture of high purity (99.999%) Ar and N2. The deposition system is a cylinder chamber equipped with four rectangular unbalanced magnetrons installed vertically around the chamber wall with a 90 degree interval to form a closed magnetic eld. The Cr target was powered using an Advanced Energy Pinnacle Plus Power supply which can be operated in both dc and middle frequency pulses conditions. The pulsed parameter was set at 100 kHz and 50% duty cycle (hereafter refer to 100/5.0). The pulsed target voltage waveform is in asymmetric pulse shape. During the positive pulse period, the target voltage is reversed to 10% of the nominal negative sputtering voltage. Mirror polished AISI 304 stainless steel coupon with the surface roughness of Ra = 30 nm and silicon (100) wafer were used as the substrates. The substrates were ultrasonically cleaned in acetone and denatured alcohol for 20 min respectively and then placed about 150 mm away from the Cr target within the chamber. After the vacuum system was evacuated below a base pressure of 1.2 10 4 Pa, the substrates were sputter etched using Ar plasma for 20 min with a pulsed bias voltage of 400 V (100 kHz and 90% duty cycle). A chromium adhesion layer (about 100 nm) was rstly deposited onto the substrates and then the CrNx coatings were deposited for 70 80 min using dc and pulsed dc sputtering with a target power density of 5.7 W/cm2 (calculated using the effective sputtering area within the sputter track, which is about 180 cm2), deposition temperatures of 250280 C and a dc substrate bias of 50 V. During coating depositions, the total gas ow rate was maintained constantly at 22 1 sccm together with a controlled pumping speed to achieve a constant working pressure of 0.27 Pa. The ow rate of the nitrogen was varied from 10 to 70% of the total ow rate with simultaneous changes in the Ar ow rate, as both controlled by the MKS 146C vacuum gauge measurement system together with separate MKS 100 sccm mass ow controllers. The nitrogen ow rate percentage will be expressed as fN2 hereafter. A Hiden Analytical Ltd EQP was used to characterize the IED in the discharged plasma. The ion energies measured by the EQP are the plasma potential relative to the ground potential. During the plasma examination, the EQP orice with a diameter of 100 m was positioned at the same location where the substrate was located during the normal deposition processes. The same tuning parameters were applied for all plasma measurements in an effort to keep a consistent comparison for the IED. The chemical compositions of the coatings were analyzed using an energy dispersive X-ray analysis (EDAX) attached to the FESEM. The EDS measurements were performed on the at coating surface (without tilt) on the coated Si substrate with the following constant parameters for all measurements: a 10 kV accelerating voltage, a 10 A probe current and a xed 10 mm working distance. The crystal structure of the coatings was characterized using monochromatic Cu-K radiation on a Siemens X-ray diffractometer (Model KRISTALLOFLEX810) operated at 30 kV and 20 mA in the GIXRD mode using a 3-degree incident angle to minimize the substrate effect. The microstructure of the coatings was characterized on the fractured cross-sections of the coatings deposited on the silicon wafer using a JSM-7000F FESEM operated at 5 kV and a Philips/FEI CM200 TEM operated at 200 kV. Cross-sectional TEM specimens were prepared by standard cutting and mechanical grinding method followed by the Ar+ ion milling process (Gatan Duo-mill). The nanoindentation hardness and Young's modulus of the coatings were evaluated using a nanoindenter (NanoIndenter XPTM, MTS Systems Corporation) equipped with a diamond Berkovich tip. Indentation

hardness (H) and Young's modulus (E) were calculated based on the model of Oliver and Pharr [24] from the loaddisplacement curves which were obtained from a constant indentation depth of 300 nm. For each sample, at least sixteen effective measurements separated by a distance of 200 m were made to obtain the statistical results. The wear properties of the coatings were evaluated by a ball on disk microtribometer (Center for Tribology, Inc) under lubricant free sliding conditions at constant room temperature of 22 2 C. The relative humidity was found to be in the range of 2025% for all tests. The wear tests were carried out along a circular track of 12 mm diameter under a load of 3 N and at a constant sliding speed of 25 mm/ s, for the duration up to 4800 cycles. A WC6 wt.% Co ball of a diameter of 1 mm was selected as the counterpart. After the wear tests, the wear tracks were examined using a Daktek surface prolometer to measure the wear volume by taking average measurements along the wear track. The wear rate of the coatings, which is dened as the wear volume of the coating divided by the applied load and the sliding length (mm3 N 1 m 1), can be subsequently calculated. 3. Results and discussion 3.1. The discharged plasma diagnostic Fig. 1 shows the IED of the 52Cr+ species in the dc and 100/5.0 pulsed plasma with a 60% fN2 measured using the EQP at the same

Fig. 1. The ion energy distributions of 52Cr+ species measured from: (a) dc magnetron discharge and (b) pulsed discharge at 100 kHz and 50% duty cycle. (The fN2 is 60% and the applied target power density is 5.7 W/cm2).

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target power density (5.7 W/cm2) and working pressure (0.27 Pa). It can be seen that the IED of 52Cr+ ions from the dc discharge shows a peak at energy of 7 eV and has low ion energy values less than 10 eV (Fig. 1a). In contrast, the 52Cr+ ions exhibit a wide range of ion energies up to 65 eV in the 100/5.0 pulsed plasma (Fig. 1b). It can be seen that the presence of the pulsed ion species is mainly from 717 eV and 22 32 eV two ion energy regions which can be correlated to the energy gain from the asymmetric positive target voltage during the reversed pulse period [20]. A very small fraction of 5065 eV high ion energy region can also be detected in the pulsed plasma. Since a 50 V dc substrate bias was applied during the depositions, the maximum ion energy in the dc discharged plasma was about 60 eV, while the maximum ion energy reached 115 eV in the 100/5.0 pulsed plasma. In addition, a signicant increase in the amount of positive ions (correlated to the areas under the IED curves) was revealed in the 100/5.0 pulsed plasma as compared to the dc discharged plasma, suggesting a higher ion ux and plasma density. The 36Ar+ and 29N+ 2 ion species exhibit similar IED spectra except for the relatively higher maximum ion energies compared to the 52Cr+ ions due to their mass difference, and will not be shown here. 3.2. Coating compositions and crystal structure The chemical compositions of the as-deposited coatings are shown in Table 1. The composition analyses indicate that the nitrogen concentration in the coatings increased as the fN2 was increased in the chamber with the simultaneously decrease in the Cr content. The oxygen concentrations in all coatings are below 4 at.%. The incorporation of Ar atoms was identied for both dc and pulsed CrNx coatings. Nevertheless, the coatings synthesized in the pulsed conditions exhibit relatively higher Ar incorporation, indicating a higher ion bombardment in the pulsed plasma. It was also found that the pulsed CrNx coatings exhibit lower N contents in comparison with those of the dc coatings synthesized at the same fN2. By increasing the fN2 to above 50% will lead to near stoichiometric compositions (N/Cr N 0.96) in CrNx coatings deposited in the dc condition, whereas a higher fN2 of 60% is necessary for obtaining similar N/Cr ratio (0.95) in the coatings prepared at 100/5.0 pulsed conditions. The GIXRD patterns of the coatings deposited at dc and pulsed conditions are presented in Fig. 2a and b, respectively. In the dc sputtering conditions (Fig. 2a), the coating deposited at 10% fN2 exhibits a bcc-Cr structure doped with small amount of N atoms, in that the Cr (110) peak at standard 44.4 (JCPDF 06-0694) was shifted to a smaller angle indicating a distortion of the Cr lattice due to the increase of the N interstitials in the bcc-Cr sites [8]. The diffraction pattern of the dc coating deposited at 20% fN2 indicates the formation of -Cr2N phase with (111), (112) and (300) reections (JCPDF 35-0803). The asymmetry peak at 42.6 indicates that there is a possible weak Cr (110) reection near 44.4, which can be attributed to the coexistence of a small amount of Cr(N) phase in the coating since the N/Cr ratio here is 0.45 (less than 0.5), as shown in Table 1. When

Table 1 The chemical compositions of CrNx coatings synthesized at various fN2 under dc and pulsed magnetron sputtering conditions (100 kHz and 50% duty cycle) DC condition fN2 [%] 10 20 30 40 50 60 70 N2 ow [sccm] 2.25 4.44 6.85 9.00 11.1 13.2 15.6 Cr [at.%] 79.23 65.5 59.89 52.27 48.44 48.19 47.21 N [at.%] 15.34 29.61 35.53 42.54 46.41 48.04 48.14 O [at.%] 3.25 2.48 2.62 3.15 3.60 2.47 2.98 Ar [at.%] 2.18 2.41 1.96 2.04 1.55 1.30 1.67 Pulsed at 100 kHz and 50% duty cycle Cr [at.%] 84.81 76.07 63.91 59.67 53.67 48.27 47.18 N [at.%] 7.68 17.27 29.21 34.24 40.37 45.70 46.33 O [at.%] 2.74 2.31 2.86 2.47 2.18 2.67 2.94 Ar [at.%] 4.77 4.35 4.02 3.62 3.78 3.36 3.55

Fig. 2. GIXRD patterns of CrNx coatings deposited at various fN2 under (a) dc magnetron sputtering and (b) pulsed magnetron sputtering (100 kHz and 50% duty cycle).

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the fN2 was increased to 30%, the dc coating exhibits a polycrystalline structure consisting of a mixture of -Cr2N and c-CrN phases as shown in Fig. 2a. Further increasing the fN2 up to 40% in the atmosphere leads to the formation of near stoichiometric c-CrN phase (JCPDF 77-2494) in the dc coatings. For CrNx coatings deposited at 100/5.0 pulsed conditions, similar crystal phase evolution from Cr(N) to -Cr2N and to a mixture of Cr2N and c-CrN, and then to the pure c-CrN with an increase in the fN2 was observed (Fig. 2b). However, it is also recognized that higher fN2 is needed to achieve these crystal phase changes in the pulsed condition in comparison with in the dc sputtering. As shown in Fig. 2b, pulsed coatings exhibit a bcc-Cr structure doped with small amount of N atoms at both 10% and 20% fN2. The formation of near stoichiometric -Cr2N phases was found at 30% fN2 in the pulsed conditions. When the fN2 was increased to 40% and 50%, the pulsed coatings contain a mixture of -Cr2N and c-CrN phases. With further increasing the fN2 up to 60%, pure c-CrN phase was observed in the pulsed coating where the N/Cr ratio reaches 0.95. In general, the crystal structure observations in the XRD patterns are in good agreement with the coating composition change. In the current studies, it is evident that the -Cr2N phase can only be formed within a very narrow range of fN2 (2030%) in the dc magnetron sputtering condition, as also reported in several references [35]. However, it was also found that the -Cr2N phase exists in a wider range of fN2 (3050%) in the 100/5.0 pulsed condition. In addition, according to the composition and XRD analysis, higher fN2 is needed for forming -Cr2N (30% fN2) and c-CrN (5060% fN2) phases in the pulsed conditions compared to 20% and 40% respectively in the dc sputtering, suggesting that the efciency of the nitrogen incorporation in the CrNx coatings is quite different in the dc and pulsed sputtering approaches. This phenomenon is possibly related to the enhanced ion bombardment from the higher ion energies and ion uxes in the pulsed plasma, which may induce extensive re-sputtering of the N atoms near the substrate region due to its smaller atomic mass and size compared to the Cr atoms, therefore decreasing the fraction of N atoms and the reactive possibility between Cr and N atoms arriving on the substrate. The energetic ion bombardment induced composition and phase differences in CrN coatings have also been observed from the previous reports on the effect of the substrate bias [25,26]. Vyas et al., found that as the substrate bias was increased from 40 to 140 V, the structure of the CrN coating completely changes from CrN to Cr2N phase, indicating a decreased N incorporation efciency at higher ion bombardment. Another observation from the XRD patterns is that the coatings containing -Cr2N phases exhibit broad diffraction peaks which is possibly related to the smaller grain sizes, e.g. 20% fN2 in the dc mode and 3040% fN2 in the 100/5.0 pulsed condition. A tendency of increase in the grain size can be seen in both pulsed and dc conditions when the near stoichiometric c-CrN phase was formed at higher fN2. 3.3. The deposition rate and microstructure of CrNx coatings Fig. 3 shows the deposition rate of the coatings as a function of the fN2 in the chamber. The deposition rate dropped as the nitrogen was increased in both dc and pulsed conditions at the same target power density and the substrate to target distance. This phenomenon can be explained by the poor N2 sputtering capability compared to Ar (reduced Ar in the chamber) and also the target poisoning effect (nitride formation on the target surface) when the N2 was increased in the system. It also can be seen that the deposition rate exhibits lower values in the pulsed conditions compared to those in the dc sputtering conditions at the same fN2, which is due to the fact that the pulsed discharge contains less effective sputtering period than in the dc mode. The cross-sectional SEM micrographs of CrNx coatings deposited with different fN2 at dc and 100/5.0 pulsed conditions are shown in

Fig. 3. The deposition rate of CrNx coatings as a function of the fN2 for dc and pulsed conditions (100 kHz and 50% duty cycle).

Fig. 4. All dc sputtered coatings exhibit columnar-type structure. The dc coating deposited at 10% fN2 which contains the bcc-Cr phase with small amount of N interstitials exhibits a columnar-type structure where the column grain size is above 100 nm (Fig. 4a). By increasing the fN2 to 20%, a denser microstructure with nearly equi-axial grains was revealed (Fig. 4b). This structure change is related to the formation of the -Cr2N phase with broad diffraction peaks as revealed in the XRD patterns (Fig. 2a). When the fN2 was increased to 30%, the dc CrNx coating exhibits a dense columnar structure consisting of short columnar grains with possible different grain sizes (Fig. 4c). As suggested in the XRD results, this coating contains a mixture of -Cr2N and c-CrN phases, which possibly comprises different sizes of the grains. Further increase of the fN2 to above 40% in the chamber will result in the formation of a large amount of c-CrN phase in the dc conditions, which normally exhibits typical Zone T columnar structure as shown in Fig. 4dg. The structural evolution in the dc sputtered CrNx coatings when the fN2 was increased is tightly connected with the phase structure and the grain size changes revealed in the XRD studies (Fig. 2a). On the other hand, the coatings deposited at 100 kHz and 50% duty cycle pulsed condition exhibit signicant structural improvements in comparison with the dc sputtered coatings (Fig. 4hn). As shown in Fig. 4h, the pulsed coating deposit with 10% fN2 exhibits a ne columnar structure which is similar to the coating deposited in the DC condition (Fig. 4a). Nevertheless, higher density and ner grain size have been achieved in the pulsed coating. With the gradual formation of the -Cr2N and a small volume fraction of c-CrN phases by increasing the fN2 in the system from 20 to 50% in the pulsed conditions, super denser microstructure and nearly equi-axial grains can be observed, as shown in Fig. 4il. When the fN2 was further increased to above 60% with the formation of large volume fraction of c-CrN phases (as shown in Fig. 2b), the pulsed coatings exhibit an increase in the grain size with the formation of short columnar grains, as shown in Fig. 4m and n. The short columnar grain structure indicates that the renucleation during the local columnar grain growth as a result of the increased ion bombardment in the PMS played an important role for the structural change. As compared to the dc sputtered CrNx coatings, the structural changes in the pulsed CrNx coatings suggest a signicant decrease in the grain size and the densication of the microstructure. This microstructure difference could be explained by two aspects. Firstly, based on the SEM and XRD studies, the CrNx coatings consisting of the -Cr2N phase exhibit a denser microstructure and ner grain size than the coatings containing c-CrN phase which typically exhibit large columnar structure. The microstructure change is consistent with several previous reports [6,26]. Therefore, the possibility of formation

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of the -Cr2N phase within a wide range of fN2 (3050%) in PMS as observed in the XRD patterns (Fig. 2b) may contribute to the structure improvement. In another more important aspect, the benecial effects of high ionization degree and density plasma with properly controlled energies from PMS for improving the structure and properties of the coatings are needed to be considered [20]. In the current study, by applying 50 V dc substrate bias on the substrate, a large amount of

ions with ion energies in the range of 60 to 80 eV together with a small fraction of ions with ion energies about 115 eV (including 50 V from the substrate bias) will be attracted towards the substrate bombarding the growing lms in the 100/5.0 pulsed conditions. This energetic bombardment can effectively transfer the energies to the adatoms, increase the adatom mobility and nucleation sites, thereby decreasing the grain size, sealing the porosities between columnar grains and densifying the coatings. In addition, renucleation on the growing

Fig. 4. Cross-sectional SEM micrographs of CrNx coatings deposited at various fN2 (1070%) in dc magnetron sputtering (a, b, c, d, e, f, g) and 100 kHz and 50% duty cycle pulsed conditions (h, i, j, k, l, m, n).

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Fig. 4 (continued ).

grains due to the ion bombardment may also account for the densication of the lm and a ne grain size in the structure [27]. In contrast, in the dc magnetron sputtering, only a small amount of ions with the energies of 50 to 60 eV (including 50 V from the substrate bias) will contribute to the effective ion bombardments, which is obviously not enough to break down the large column growth, seal the porosities and achieve high densities in the coatings. This second effect is further proven in the TEM study. Crosssectional TEM micrographs and insert SAED (selected area electron diffraction) patterns of CrN coatings deposited at 60% fN2 in dc and 100/5.0 pulsed conditions are presented in Fig. 5a and b respectively. The structure of the coating deposited by continuous dc is characterized as a clear columnar structure with average column width of about 2030 nm. The voids between the columnar grains (indicated by the dark strips) are clearly identied (Fig. 5a). The discontinued diffraction rings in the SAED pattern conrm the presence of relatively large grains of CrN B1 NaCl reections. In contrast, the pulsed CrN coating exhibits a less pronounced columnar structure (Fig. 5b). The voids between the column grains become less remarkable, suggesting a denser microstructure was obtained. In addition, the SAED pattern shows more continuous rings without sharp spots compared to the dc coating, indicating ner grains (b 10 nm from the micrograph observation) in the pulsed coating.

Besides the positive effect of the energetic deposition in PMS, it is also recognized that excessive ion bombardment will induce the accumulation of the residual stress and point/line defects in the growing coatings, which is detrimental to the coating toughness and adhesion [5,20]. The plasma analysis in the current study indicated that only a very small fraction of ions with high energies in the range of 100115 eV were presented in the 100/5.0 pulsed plasma, while a large fraction of ions come from 5080 eV (adding 50 V from the substrate bias), suggesting a possible small incorporation of stress and defects in the growing coatings. 3.4. Mechanical and tribological properties The nanoindentation hardness values of CrNx coatings deposited by dc and PMS as a function of fN2 are presented in Fig. 6. As can be seen, the hardness of the coatings with an increase in the fN2 exhibits very similar trend for both dc and pulsed conditions. With the incorporation of a small fraction of N (fN2 = 10%), a rapid increase in the hardness from 1011 GPa in the pure Cr coatings to 2022 GPa in the Cr(N) coatings were observed in both conditions, which is due to the formation of the covalent CrN bonds. The highest hardness values of 25 GPa and 31 GPa were found at 20% and 30% fN2 in the dc and 100/ 5.0 pulsed conditions respectively, which correspond to the formation

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Fig. 6. The hardness of CrNx coatings as a function of fN2 produced under dc and pulsed magnetron conditions (100 kHz and 50% duty cycle).

were presented in the CrNx coatings is consistent with the previous reports [6]. Furthermore, the hardness results conrm that when the fN2 exceeded 20%, the coatings deposited in the pulsed conditions exhibit superior hardness values than the coatings produced by dc sputtering. The enhancement of hardness in the pulsed coatings was probably attributed to their higher density, ner grain size and also possible higher residual stress generated from higher ion bombardment.

Fig. 5. Cross-sectional TEM micrographs of CrNx coatings deposited at 60% fN2 in (a) dc magnetron sputtering and (b) pulsed magnetron sputtering (100 kHz and 50% duty cycle).

of a large volume fraction of -Cr2N phases as identied in the XRD pattern. This is probably because the coatings consisting of pure -Cr2N phase exhibit higher density and ner grain size than the other mixture phase or pure c-CrN coatings, as shown in the SEM observations (Fig. 4). It was also well recognized that the -Cr2N phase is more covalent than the c-CrN phase leading to higher intrinsic hardness than that of the cubic phases [28]. After that, a slightly decrease in the hardness can be seen in both conditions when the coatings consist a mixture of -Cr2N and c-CrN phases when the fN2 is in the range of 3040% in the dc condition, and 4050% in the pulsed condition. In both cases, the hardness values of CrNx coatings were slightly increased again after 40% and 60% fN2 respectively accompanied with the formation of near stoichiometric c-CrN phase in the coatings. The slightly drop of the hardness when mixture phases

Fig. 7. (a) The coefcient of friction and (b) the wear rate of CrNx coatings as a function of fN2 prepared in dc and pulsed magnetron conditions (100 kHz and 50% duty cycle).

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The coefcient of friction (COF) and the wear rates of CrNx coatings deposited under dc and pulsed conditions sliding against a WC6%Co ball in the lubricant free condition at a normal load of 3 N are plotted in Fig. 7a and b respectively. All COF values were measured from the steady sliding state between the counter part and the coatings. The COF was found to rstly decrease with an increase in the fN2 and reached the lowest values of 0.47 at 40% fN2 and 0.36 at 50% fN2 in the dc and pulsed coatings respectively, and then increase again with a further increase in the fN2 (Fig. 7a). By examining the wear rate after the sliding tests, it was found from Fig. 7b that the wear rate evolution as a function of the fN2 followed the trend of the COF. As the fN2 is higher than 20%, the wear rate of CrNx coatings decreased rapidly and exhibited low values of about 3 10 6 mm3 N 1 m 1 in the dc CrN coatings and 1.66 to 2 10 6 mm3 N 1 m 1 in the pulsed coatings at 4050% fN2 (Fig. 7b). The XRD patterns shown in Fig. 2 indicate the presence of the mixture of -Cr2N and c-CrN phases at 30% fN2 in the dc sputtered coatings and at 3050% fN2 in the pulsed coatings. Therefore, the decrease in the COF and wear rate is possibly associated with the presence of -Cr2N and c-CrN mixture in the coatings. However, with the formation of single c-CrN phase at higher fN2 percentages, the COF and the wear rate of the coatings increased again in both conditions. It was also evident that the COF and the wear rate of all pulsed coatings were lower than those of the dc coatings prepared at the same fN2. This behavior emphasizes that the denser structure, ner grain size, and higher hardness, observed in the pulsed CrNx coatings will result in the improved wear resistance compared to the dc sputtered coatings. 4. Conclusions Chromium nitride (CrNx) coatings were prepared using a CFUBMS system under dc and middle frequency pulsed condition (100 kHz and 50% duty cycle) with different nitrogen ow rate percentages (fN2) in the system. It was found that the crystal phases changed from bcc-Cr structure doped with small amount of N atoms to pure -Cr2N, and to a mixture of -Cr2N and CrN phases, and then to the pure c-CrN with an increase in the fN2 for both dc and pulsed conditions. However, it is also recognized that the N2 incorporation efciency in the PMS is lower than that in the dc condition, therefore higher fN2 is needed in the pulsed sputtering for the corresponding crystal structure changes observed in the dc sputtering. The CrNx coatings consisting of near stoichiometric -Cr2N phase exhibit the highest hardness in both dc and pulsed conditions, while the low coefcient of friction was found in the coatings containing a mixture of -Cr2N and c-CrN phases. Plasma examination showed that a large amount of ions with a wide range of ion energies (mainly from 1030 eV) were identied in the 100 kHz and 50% duty cycle pulsed plasma compared to lower ion ux and energy (10 eV) in a dc discharged plasma. By applying 50 V dc substrate bias, the increased ion uxes and energies in the pulsed plasma could be accelerated towards the substrate to enhanced the

ion bombardment, which can be utilized to increase the adatom mobility, increase the nucleation sites, and seal the void columnar grain boundaries, thereby resulting in denser structure and ner grain size in the pulsed coatings. The improved microstructure contributed to the improvements in the hardness and wear resistance of pulsed CrN coatings, where the high hardness values above 30 GPa were obtained when the fN2 is in the range of 3040% and a low COF of 0.36 and a wear rate of 1.66 to 2 10 6 mm3 N 1 m 1 were found in the coating deposited with 4050% fN2. Acknowledgements The authors are grateful for the nancial support of this research program from DOE-OIT, ATI, and the North American Die Casting Association (NADCA). References
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