A comparison of the oxidation behavior of CrN lms deposited using continuous dc,
pulsed dc and modulated pulsed power magnetron sputtering
Jianliang Lin a, , Ningyi Zhang a , William D. Sproul a, b , John J. Moore a a Advanced Coatings and Surface Engineering Laboratory (ACSEL), Department of Metallurgical and Materials Engineering, Colorado School of Mines, Golden, CO, 80401, USA b Reactive Sputtering, Inc, 2152 Goya Place, San Marcos, CA, 92078 USA a b s t r a c t a r t i c l e i n f o Article history: Received 3 June 2011 Accepted in revised form 16 January 2012 Available online 26 January 2012 Keywords: CrN lms Modulated pulsed power (MPP) magnetron sputtering High power pulse magnetron sputtering (HPPMS) High power impulse power magnetron sputtering (HIPIMS) Oxidation Activation energy The study is aimed at comparing the oxidation behavior of the stoichiometric CrN lms deposited by contin- uous dc magnetron sputtering (dcMS), mid-frequency pulsed dc magnetron sputtering (PMS), and modulat- ed pulsed power (MPP) magnetron sputtering techniques in a closed eld unbalanced magnetron sputtering system. These as-deposited CrN lms exhibited a cubic structure and similar stoichiometric compositions, but with different microstructures and residual stresses. After annealing in the ambient air from 600 to 1000 C, the changes in the crystal phase, microstructure, and hardness of the lms were characterized using X-ray diffraction, scanning electron microscopy, energy dispersive X-ray spectroscopy line scan, and nanoindenta- tion. The oxidation activation energies of the lms were calculated using Arrhenius equation. It was found that the MPP CrN lm exhibited superior oxidation resistance than dcMS and PMS CrN lms. After annealing at 900 C, the MPP CrN lm exhibited an extremely dense structure and the cubic phase was well maintained. On the other hand, the dcMS and PMS CrN lms were severely oxidized into a porous structure with the de- velopment of -Cr 2 N and Cr 2 O 3 phases and a rapid degradation of the cubic phase after 700 and 800 C, re- spectively. The results indicate that all lms showed a parabolic oxidation rate below 900 C. The oxidation activation energies for the dcMS, PMS and MPP CrN lms are 116 kJ/mol, 141 kJ/mol, and 195 kJ/mol, respec- tively. The better oxidation resistance of the MPP CrN lm is attributed to its dense microstructure and low residual stress. Published by Elsevier B.V. 1. Introduction As one of the transition metal nitride lms, CrN lms have been extensively studied for material protection due to their high hard- ness, good wear resistance, chemical inertness, and good thermal sta- bility. Magnetron sputtering is a convenient and widely used technique for CrN lm depositions. The CrN lms have been widely deposited using continuous dc magnetron sputtering (dcMS) [15], mid-frequency pulsed dc magnetron sputtering (PMS) [6] and recent- ly high power pulsed magnetron sputtering (HPPMS) techniques [7,8]. The oxidation behavior and thermal stability of the CrN lms deposited by dcMS and PMS have been widely reported [15]. In gen- eral, the cubic CrN (c-CrN) lm degraded rapidly after 600 C through the formation of hexagonal Cr 2 N (-Cr 2 N) phase by the outward dif- fusion of N [9,10]. This process was accompanied by the grain growth and a decrease in the lm residual stresses and defects (e.g. intersti- tials and dislocations). The observation of the Cr 2 O 3 formation on the CrN lm surface was widely reported from 500600 C, which was dominated by the outward diffusion of Cr and inward diffusion of O through the formed Cr 2 O 3 layer [11,12]. The oxidation rate was found to t a parabolic time law. The oxidation resistance and thermal stability of nanostructured lms depend on many factors, including the lmchemical composition, microstructure, residual stress, and defect density formed during the deposition process. Djouadi et al. [13] have shown that the stoichiomet- ric c-CrN lms exhibited better oxidation resistance and thermal stabil- ity than the nitrogen decient -Cr 2 N lms because of the existence of metallic Cr in the Cr 2 N lms. From a structural point of view, since the oxidation kinetics of a nanocrystalline lm were dominated by the out- ward cationic diffusion and inward diffusion of O through the grain boundaries, the activation energy for the diffusion is largely dependent on the density, grain boundary, and grain size of the as-deposited lms. It is not a surprise that the cationic and cathodic diffusions need much higher activation energies to pass through a dense lmthan in a porous lm. In general, the development of compressive residual stresses and the incorporation of certain levels of defects in the hard lms can ef- fectively increase the hardness of the lms. However, from a thermo- dynamic point of view, these high residual stress and defect densities also result in an intrinsic instability of the microstructure of the lms at evaluated temperatures. Veprek [14] has pointed out that a num- ber of superhard lms lost their superhardness whenever such lms Surface & Coatings Technology 206 (2012) 32833290 Corresponding author. Tel.: +1 303 273 3178; fax: +1 303 273 3795. E-mail address: jlin@mines.edu (J. Lin). 0257-8972/$ see front matter. Published by Elsevier B.V. doi:10.1016/j.surfcoat.2012.01.033 Contents lists available at SciVerse ScienceDirect Surface & Coatings Technology j our nal homepage: www. el sevi er . com/ l ocat e/ sur f coat are annealed to a temperature higher than the deposition tempera- ture due to the relaxation of the compressive stress and defects (e.g. interstitials and dislocations) originating from the energetic ion bom- bardment during deposition. Mitterer [15] and Mayrhofer [16] sug- gested that an introduction of high defect densities to obtain superhard lms might result in reduced thermal stability because of the lower thermal activation needed to start recovery in such structures. Considering the above factors, one of the effective approaches to increasing the thermal stability of nanostructured lms is to increase the density of the lms while reducing the stresses and defects in the lms by carefully controlling the deposition parameters, e.g. the ion bombardment energies and ion uxes. Nevertheless, these plasma conditions strongly depend on the sputtering techniques. In recent years, HPPMS (also named high power impulse magnetron sputtering (HIPIMS)) [1720] and its alternative technique modulated pulsed power (MPP) magnetron sputtering [2124] were developed to gen- erate a high degree of ionization of the target species by using pulsed high peak power on the target. It was suggested that the high instan- taneous deposition rate during the on time of the high power pulse leads to high initial nucleation island densities, and the intense ion ir- radiation of the growing lm by the high metal ion ux providing densication via ion bombardment-induced adatom migration [25]. Ehiasarian et al. [26] improved the structure and wear resistance of CrN lms deposited by HIPIMS compared with arc bond sputtering. Recently, Lin et al. [7] also observed improvements in the density, ad- hesion, mechanical, and tribological properties of CrN lms deposited by MPP compared with dcMS and PMS without using external bias and heating. Thick and dense CrN lms (up to 55 m) have been suc- cessfully deposited at a high deposition rate using the MPP technique [27]. In comparison with the traditional HPPMS/HIPIMS technique, the MPP technique has a higher deposition rate [22,28]. The MPP plasma exhibited large metallic ion uxes. These ions show a major peak ion energy of 25 eV and a small ion energy tail with the maximum ener- gy less than 30 eV [7,23]. The large metallic ion ux in the MPP plas- ma provides enhanced ion bombardment on the growing lm to achieve a fully dense structure. Nevertheless, the residual stress and the defect density of the MPP lms can be maintained low because of the low ion energies of the majority of the ions [7]. As discussed previously, these factors are critical for the thermal stability of nano- structured hard lms. Therefore, it is expected that the MPP lms may exhibit a different oxidation behavior and thermal stability compared to the lms deposited by traditional magnetron sputtering techniques (e.g. dcMS and PMS). Although recent research has demonstrated the improved microstructure, adhesion, mechanical and tribological properties of several hard coating systems deposited by the HPPMS/ HIPIMS and MPP techniques as compared to the traditional magne- tron sputtering techniques, no studies have been reported on the comparison of the oxidation resistance and thermal stability of these lms. Therefore, the aim of this study is to use the CrN lm as an exam- ple to compare the oxidation behavior of the nanostructured lms deposited by dcMS, PMS, and MPP techniques with a similar stoichi- ometry and thickness, but with different microstructures and internal stresses. The CrN lms were annealed from 600 C to 1000 C in the ambient air. After the oxidation tests, changes in the crystal phase, microstructure, oxide layer thickness and hardness of the CrN lms were characterized and compared. The oxidation activation energy of these CrN lms was obtained using the Arrhenius equation. 2. Experimental details CrN lms were deposited on AISI 304 stainless steel coupons and (100) silicon wafers in a closed eld unbalanced magnetron sputter- ing (CFUBMS) system by reactively sputtering a Cr target (100 mm300 mm) in an Ar:N 2 mixture. The deposition system is a cylindrical chamber equipped with two unbalanced magnetrons (Teer Films, LTD.) of reversed magnetic polarities, which were placed opposite with a distance of 240 mm to form a closed magnetic eld. The schematic drawing and detailed descriptions of the CFUBMS sys- tem can be found in Refs. [24,28]. The substrates were ultrasonically cleaned in acetone and alcohol for 15 min respectively. The substrates were installed at about 100 mm away from the Cr target. A base pres- sure below 1.310 4 Pa was reached prior to all depositions. The substrates were sputter etched by Ar plasma bombardment at a 1.34 Pa working pressure using a pulsed dc bias of 500 V (100 kHz and 90% duty cycle) for 30 min. A thin Cr adhesion layer (100150 nm) was deposited on the sub- strates. Then the CrN lms were deposited using dcMS (Pinnacle, Ad- vanced Energy Inc.), PMS (Pinnacle Plus, Advanced Energy Inc.), or MPP (SOLO/AXIS-180 Pulsed DC Plasma Generator, Zpulser LLC.) power sources. Table 1 summarizes the deposition conditions. For the dcMS and PMS depositions, an average target power (P a ) of 3 kW was used. In the PMS depositions, an asymmetric bipolar pulsing voltage was ap- plied on the Cr target with the pulsing parameters of 100 kHz and 60% duty cycle (the target voltage was reversed to 10% of the nominal negative sputtering voltage during the positive pulse period). In the MPP depositions, the pulse length was 1000 s, which contains a 500 s weak ionization stage and a 500 s strong ionization stage [7]. The peak voltage (V p ), peak current (I p ) and peak power (P p ) on the target during the strong ionization stage in the pulse were 575 V, 190 A and 95 kW, respectively, whereas P a was maintained constantly at 3 kW. The repetition frequency was 73 Hz, which is re- lated to the selected P p and P a . A 50 V DC substrate bias voltage was applied for all depositions (Axis, Zpulser LLC.). During the depo- sitions, high purity Ar and N 2 (99.999%) were introduced into the sys- tem separately using MKS mass ow controllers. The working pressure, which was measured by a high precision capacitance ma- nometer, was kept constant at 0.67 Pa. The total gas ow rate was 62 sccm. The N 2 ow rate was maintained at 50% of the total ow rate. High temperature oxidation tests were carried out in a CARBOLITE type 301 furnace. The samples were annealed in an ambient air at el- evated temperatures from 600 to 1000 C for 1 h. All samples were Table 1 The deposition conditions for the dcMS, PMS and MPP CrN lms. Pulsing parameters P a [kW] P p [kW] I a [A] I p [A] V a [V] V p [V] I d [A/cm 2 ] I sub [mA/cm 2 ] Pressure [Pa] Ar:N 2 Bias [V] dcMS N/A 3.0 7.06 425 0.04 1.5 0.67 1:1 50 PMS 100 kHz and 60% duty cycle 3.0 8.92 336 0.05 4.2 0.67 1:1 50 MPP 73 Hz and 7.3% duty cycle 3.0 95 83 190 463 575 1.10 215 0.67 1:1 50 P a and P p are the average and peak target power. I a and I p are the average and peak target current in one pulse length. V a and V p are the average and peak target voltage. I d is the peak target current density during the pulse. I sub is the substrate peak ion current density during the pulse. 3284 J. Lin et al. / Surface & Coatings Technology 206 (2012) 32833290 cooled down to room temperature within the furnace. Special speci- mens were made by depositing lms on six faces of small pieces of steel substrates. The weight gain of these lms was measured using simultaneous thermal analysis (STA) from 600 to 900 C in the ambi- ent air for 10 h. The thermal ramping to the isothermal oxidation temperature was set to 40 K min 1 for all samples in a 55 sccmow- ing Ar atmosphere in order to avoid premature lm oxidation. When the oxidation isothermal temperature was reached, a ow of air (30 sccm) was used as the background atmosphere for the ten hour isothermal test. The oxidation rate constant (k p ) was obtained from the weight gain as function of the time of exposure at high tempera- tures. Then the oxidation activation energy (E a ) of the lms was cal- culated by plotting the inverse temperature versus the natural log of the oxidation rate using the Arrhenius equation. ln k p
ln A E a R 1 T where R is the gas constant, and T is the isothermal temperature. Then E a can be obtained from the slope of the curve. The crystal structure of the lms was characterized by X-ray dif- fraction (XRD) using a Siemens diffractometer (Model KRISTALLOFLEX-810) operated with K
Cu radiation (20 kV and
30 mA) in the conventional BraggBrentano mode. The residual stress of the lms was measured by glancing incident angle XRD (GIXRD) in the same X-ray diffractometer. The chemical composition of the as- deposited lms was investigated by X-ray photoelectron spectrosco- py (XPS) (PHI model 5600LS) using an Al K
X-ray source. The micro-
structure of the lms was characterized by a eld-emission scanning electron microscope (SEM) (JSM-7000F) using a 5 kV operation volt- age. An energy dispersive spectroscopy (EDS) line scan was carried out along the cross-section of the annealed lms to verify the oxide layer. The hardness of the lms was measured by a nanoindenter (NanoIndenter XPTM, MTS Systems Corporation) using a diamond Berkovich tip. The hardness of the annealed CrN lms was measured as a function of the indentation depth (up to 500 nm) to distinguish the hardness of the surface oxide layer and the underlay lm. 3. Results 3.1. Microstructure and properties of the as-deposited CrN lms Fig. 1 shows the cross-sectional SEM micrographs of the as- deposited CrN lms. The dcMS CrN lm exhibited a porous columnar grain structure, which contains long columnar grains and clear grain boundaries throughout the lm thickness. The fractured morphology of the dcMS CrN lm indicates an intergranular fracture along the co- lumnar grains due to the low lm density and weak boundary bond- ing strength between the grains. The PMS CrN lm showed a dense microstructure, in which ne granular grains were developed throughout the lm thickness. In contrast, the MPP CrN lm exhibited a dense and disordered short columnar grain structure. The bound- aries between the short columnar grains along the coating thickness are not as clear as those in the dcMS lm. The laminated features ob- served from the fractured cross-section of the MPP CrN lm indicate a transgranular fracture across the crystals due to the high density and strong boundary bonding strength between the grains [29]. In this study, the sequence of the deposition rate from high to low is dcMS, MPP and PMS, which is similar to the results from an earlier study [7]. Fig. 2 shows the XRD patterns of the as-deposited dcMS, PMS and MPP CrN lms and after annealing at different temperatures. As shown in Fig. 2, all as-deposited lms exhibit a face centered cubic (FCC) CrN (c-CrN) structure (circle symbol) (JCPDS 110065). The dcMS lm shows strong (111) and (200) peaks, and weak (220) and (311) peaks (Fig. 2A). The PMS lm exhibits a strong (111) peak and weak (200) and (311) peaks (Fig. 2B). In contrast, the MPP lm shows a strong (311) peak and weak (111) and (200) peaks (Fig. 2C). The peaks of the PMS lm shifted to a lower angle than the dcMS and MPP lms. Since the N/Cr ratios of the lms are similar, the larger shift of the diffraction peaks in the PMS CrN lm is attributed to its higher residual stress (Table 2), which was possibly generated by the high energy ion bombardment from the PMS plas- ma, which contains a wide range of ion energy distribution for gas and metal ions (e.g. the maximum ion energy may reach hundreds of eV) [36]. The grain sizes of the as-deposited dcMS, PMS and MPP CrN lms were 24.5 nm, 18.9 nm and 14.1 nm respectively, as calcu- lated using the Scherrer equation [30]. The thickness of the lms varied in a small range of 2.8 to 3.1 m. As summarized in Table 1, all lms have a near stoichiometric composition with an N/Cr ratio in the range of 0.94 to 0.98. The Ocontent in the lms is less than 5 at.%. The compressive residual stresses of the dcMS, PMS, and MPP CrN lms are 2.0 GPa, 4.5 GPa, and 2.5 GPa, respective- ly. The hardness and H/E ratio (resistance against elastic strain to fail- ure) of the dcMS CrN lm are 23 GPa and 0.07, respectively. The PMS and MPP CrN lms showed similar hardness values of 28 GPa. And the MPP CrN lm exhibited the highest H/E ratio of 0.087. Fig. 1. Cross-sectional SEM micrographs of the as-deposited CrN lms deposited using (A) dcMS, (B) PMS, and (C) MPP techniques. 3285 J. Lin et al. / Surface & Coatings Technology 206 (2012) 32833290 3.2. Microstructure of the lms after annealing After annealing at 600 C, the c-CrN peaks of all three lms shifted toward the standard positions due to the stress and defect relaxations (for interstitials and dislocations) at elevated temperatures. Strong diffraction peaks associated with -Cr 2 N phase (down triangle sym- bol) (JCPDS 350803) and a small amount of Cr 2 O 3 phase (square symbol) (JCPDS 381479) were detected in the dcMS CrN lm (Fig. 2A). However, nearly no crystalline oxide diffraction peaks were detected in the PMS and MPP CrN lms after annealing at 600 C. The XRD patterns of the PMS lm exhibited a strong c-CrN phase with the appearance of a small amount of -Cr 2 N phase (Fig. 2B). In contrast, the c-CrN phase was well maintained and al- most no -Cr 2 N phase was detected in the MPP CrN lm after anneal- ing at 600 C (Fig. 2C). The cross-sectional SEM micrographs and the EDS line scan of the lms after annealing from 700 C to 1000 C are shown from Figs. 3 to 6, respectively. After annealing at 700 C, the XRD pattern of the dcMS lm showed dominant -Cr 2 N, Cr 2 O 3 , and weak Cr phases (JCPDS 060694) (diamond label), accompanied with a rapid decrease in the c-CrN phase (Fig. 2A). The SEM image conrms the grain growth in the top half of the dcMS lm with the development of a 200 nm oxide layer on the surface (EDS line scan) (Fig. 3A). For the PMS CrN lm, the intensity of the -Cr 2 N (110) and (111) peaks increased signicantly with a rapid decrease in the c-(111) peak after annealing at 700 C (Fig. 2B). In contrast, only a small amount of -Cr 2 N phase was formed in the MPP lm (Fig. 2C). As compared to the as- deposited lms, the increase in the grain size of the PMS and MPP lms is evident from the SEM images (Fig. 3B and C). The EDS line scan shows a less than 100 nm thin oxide layer has been formed on the PMS and MPP lm surface after annealing at 700 C, which can hardly be seen from the cross-sectional SEM images. However, this thin oxide layer was conrmed from the XRD patterns, which show small Cr 2 O 3 (012) and (104) peaks (Fig. 2B and C). The development of the Cr 2 O 3 phase on the CrN lm surface after annealing in the air from 600 to 700 C has been mainly explained by the outward diffusion of Cr species [11,12]. The phase transformation of the CrN lms from c-CrN to -Cr 2 N upon heat treatment as early as 500600 C has also been reported [31]. The mechanisms of this phase transformation have been attributed to the stress relaxation [31] and outward diffusion of N in the near surface region during annealing [10]. Therefore, the residual stress level and the density of the lms play an important role in determining the c-CrN to -Cr 2 N phase transformation. The relatively low density of the dcMS CrN lm and the relatively high residual stress in the PMS CrN lm probably are related to their earlier phase transformation from c-CrN to -Cr 2 N at elevated temperatures than the dense MPP CrN lm. After annealing at 800 C, the intensities of the -Cr 2 N and Cr 2 O 3 phases further increased in the dcMS CrN lms, while the c-CrN phase completely disappeared (Fig. 2A). Similar to the 700 C annealed PMS lm, the 800 C annealed PMS lm still exhibited a mixture of the c-CrN and -Cr 2 N phases with a slight increase in the Cr 2 O 3 peak intensities (Fig. 2B). For the MPP CrN lm, small -Cr 2 N (110) peak was observed with the disappearance of the c-CrN (111) peak after 800 C (Fig. 2C). Nevertheless, the MPP CrN lm still Fig. 2. XRD patterns of the as-deposited (A) dcMS, (B) PMS, and (C) MPP CrN lms and after annealing at different temperatures (the peaks indexed as S are arisen from the substrate). Table 2 The properties and oxidation temperatures for the dcMS, PMS and MPP CrN lms. Technique N/ Cr Thickness [m] Gain size (As-dep) [nm] Residual stress [GPa] Hardness, H [GPa] Young's modulus, E [GPa] H/E Phase formation T [C] Stable T for cubic CrN [C] -Cr 2 N Cr 2 O 3 dcMS 0.98 2.8 24.5 2.0 23.0 328 0.070 >600 >600 b700 PMS 0.94 2.9 18.9 4.5 27.8 338 0.082 >600 >700 b800 MPP 0.95 3.1 14.1 2.5 28.2 323 0.087 >700 >700 b900 3286 J. Lin et al. / Surface & Coatings Technology 206 (2012) 32833290 exhibited a strong c-CrN (311) peak, which demonstrated its excel- lent thermal stability (Fig. 2C). There was a slight increase in the Cr 2 O 3 peaks of the 800 C annealed MPP CrN lm. As shown in Fig. 4, a dense Cr 2 O 3 layer was formed and separated from the underlay large grains by a thin and porous region in the dcMS and PMS lms after annealing at 800 C. The formation of a po- rous region under the top dense oxide layer in the CrN lms is mainly due to the outward diffusion of Cr species to the surface, as widely reported [11]. As shown in Fig. 4A and B, the top half of the dcMS and PMS CrN lms exhibited a more porous structure with a larger grain size than the bottom half of the lms. In contrast, the interface between the top oxide layer and the MPP lm after annealing at 800 C is dense. Moreover, an extremely dense microstructure under the top oxide layer can be observed from the MPP CrN lm after annealing at 800 C (Fig. 4C). After annealing at 900 C, the intensity of the -Cr 2 N peaks de- creased signicantly for the dcMS CrN lm, whereas the intensity of the Cr 2 O 3 peaks increased continuously (Fig. 2A). The c-CrN phase in the PMS CrN lm disappeared after annealing at 900 C. The PMS CrN lm also showed a signicant decrease in the -Cr 2 N phase with a fur- ther increase in the Cr 2 O 3 peaks (Fig. 2B). As shown in Fig. 5A and B, the SEM images and the EDS line scan conrmed that the dcMS and PMS CrN lms were severely oxidized after annealing at 900 C. The thick- ness of the oxide layer on the surface is about 600 nm and 700 nm, which can be clearly indentied from the SEM images (Fig. 5). The structure of the dcMS and PMS lms under the top oxide layer became extremely porous (Fig. 5A and B). The EDS line scan conrms that there is almost no N content in the surface oxide region, and the N is reduced in the lms under the oxide layer, especially for the PMS lm. The large columnar grain boundaries in the dcMS CrN lm possibly lead to the fast diffusion of N outward from the lms. Although the decreased grain size favors the improvements in the mechanical properties, the large inter-crystalline volume fraction (e.g. grain boundaries) in the PMS CrN lm could also act as outward diffusion paths for N atoms from thermodynamic point of view. In contrast, the MPP CrN lm still maintained an excellent oxida- tion resistance at 900 C. The XRD pattern conrmed that the c-CrN (311) peak was well maintained after annealing at 900 C (Fig. 2C). This is further justied by the SEM view of the extremely dense mi- crostructure developed under the top 600 nm dense oxide layer, as shown in Fig. 5C. The densication of the MPP CrN lm at elevated temperatures was mainly attributed to the kinetic growth of the CrN grains with a decrease in the grain boundary areas by the energy reduction. Such a dense microstructure in the MPP lm could have a strong barrier effect for slowing down the outward diffusion of the Cr and N species and the inward attack from the oxygen. Consequent- ly, the MPP CrN lm showed excellent phase stability. As the oxidation temperature reached 1000 C, Fig. 2A shows that the phases in the dcMS CrN lms are composed of Cr 2 O 3 and Cr, while the -Cr 2 N phase completely disappeared. The EDS line scan detected high O content and barely any N content throughout the lm thick- ness, which indicates the dcMS CrN lm was completely oxidized (Fig. 6A). The PMS CrN lm was also severely oxidized at 1000 C. The major phase in the PMS lm was Cr 2 O 3 with a small amount of Fig. 3. Cross-sectional SEM micrographs and corresponding EDS line scans of (A) dcMS, (B) PMS, and (C) MPP CrN coatings after annealing at 700 C. Fig. 4. Cross-sectional SEM micrographs and corresponding EDS line scans of the (A) dcMS, (B) PMS, and (C) MPP CrN coatings after annealing at 800 C. 3287 J. Lin et al. / Surface & Coatings Technology 206 (2012) 32833290 -Cr 2 N phase (Fig. 2B). As shown in Fig. 6B, an extremely porous mi- crostructure was formed under the top fully developed oxide layer. The thickness of the complete oxidized region in the PMS CrN lm is about 2 m accompanied with a complete reduction of N in this re- gion. However, a 1.5 m thick region from the bottom of the PMS lm exhibited a granular grain structure without O content, which is at- tributed to the remaining -Cr 2 N in the lm (Fig. 6B). In contrast, after annealing at 1000 C, the XRD study conrmed that the MPP CrN lm contained a mixture of -Cr 2 N and Cr 2 O 3 phases (Fig. 2C). The c-CrN phase was completely transferred to - Cr 2 N phase, which was now the major phase in the lm. The SEM image and EDS line scan showed that a two layered structure was formed in the MPP CrN lm, which includes a 1.5 m polycrystalline Cr 2 O 3 layer and the underlay dense MPP CrN x lm(Fig. 6C). The inter- face between the top oxide layer and the lm became porous. The EDS line scan showed that N was completely depleted in the top oxide layer, but it was maintained well in the intact lm. In addition, no oxygen was detected in the underlay dense lm. These results con- rmed that the inward diffusion of O and the outward diffusion of Cr and N were effectively slowed down in the dense MPP CrN lm. 3.3. Mechanical properties The hardness of the dcMS, PMS and MPP CrN lms was plotted as a function of the oxidation temperature as shown in Fig. 7. After annealing at 600 C for 1 h, the hardness of the dcMS, PMS, and MPP CrN lms dropped down to 18 GPa, 23 GPa and 25 GPa, respectively. The decrease in the lm hardness is mainly due to the stress relaxation, annealing of the defects to the grain boundaries, and also the grain growth. After 600 C, the hardness of all lms de- creased rapidly as the oxidation temperature was further increased. The hardness of the dcMS and PMS CrN lms dropped down to 43% and 45% of the as-deposited hardness after annealing at 800 C. Fig. 6. Cross-sectional SEM micrographs and corresponding EDS line scans of the (A) dcMS, (B) PMS, and (C) MPP CrN coatings after annealing at 1000 C. Fig. 7. Hardness of the dcMS, PMS and MPP CrN lms as a function of the oxidation temperature. Fig. 5. Cross-sectional SEM micrographs and corresponding EDS line scans of the (A) dcMS, (B) PMS, and (C) MPP CrN coatings after annealing at 900 C. 3288 J. Lin et al. / Surface & Coatings Technology 206 (2012) 32833290 Nevertheless, the MPP CrN lm retained 67% of the as-deposited hardness after annealing at 800 C. 3.4. Oxidation activation energy Plots of the square of mass gains per area (m) 2 /cm 4 at different temperatures for the MPP CrN lms with time are shown in Fig. 8A. It can be seen that the MPP CrN lms exhibited a parabolic oxidation rate at the temperature range from 700 C to 900 C. The dcMS and PMS CrN coatings also exhibited a parabolic oxidation rate (not shown here). The parabolic oxidation rate constant (k p ) at each iso- thermal oxidation temperature (T) was obtained from the slope of the curves using the equation: m =cm 2
2 k p t: Fig. 8B shows the Arrhenius plots of ln(k p ) as a function of 1/T for dcMS, PMS and MPP CrN lms. The oxidation E a obtained from the slope of plots using the Arrhenius equation for the dcMS, PMS and MPP CrN lms are 116 kJ/mol, 141 kJ/mol and 195 kJ/mol, respective- ly. These E a values are comparable to the literature reported values for the CrN lms in a wide range of 98 to 251 kJ/mol [3235]. 4. Discussion The above results have shown that the dcMS, PMS and MPP CrNlms exhibited different oxidation behaviors in the ambient air. As summa- rized in Table 2, the MPP CrNlmexhibits the highest stable temperature for c-CrNphase up to 900 C. The MPP CrNlmalso requires higher tem- peratures for the -Cr 2 N phase formation as compared to the dcMS and PMS CrN lms. Therefore, we conclude that the CrN lms deposited using the MPP technique exhibited superior oxidation resistance as com- pared to the lms deposited by the traditional dcMS and PMS techniques. Since the chemical composition and thickness of the CrN lms are similar, the oxidation behavior of the CrN lms is largely dependent on the microstructure, texture and residual stress of the lms, which are strongly affected by the sputtering techniques. It has been shown that the dcMS, PMS and MPP CrN depositions generated different ion energy distributions and ion uxes in the plasma [7]. The dcMS plasma exhibited low ion energies (b15 eV) and low ion uxes; the PMS plasma exhibited a wide range of ion en- ergies (>100 eV) and a moderate level of ion uxes; and the MPP plasma exhibited low ion energies (b30 eV) but an extensive amount of ion ux, especially for the metal ions. Therefore, the development of different microstructures and residual stresses of the CrN lms is related to different plasma properties (ion energy and ion ux) of the dcMS, PMS and MPP plasmas. An open columnar structure was developed in the dcMS lm due to insufcient ion bombardment (Fig. 1A). The high ion energies of the PMS plasma and the high metal ion uxes of the MPP plasma provided enhanced ion bombard- ment on the growing lms, which formed a dense and less columnar grain featured microstructure. Nevertheless, the large kinetic ion en- ergies in the PMS plasma (e.g. >100 eV) also easily generated higher residual stresses and defect densities in the PMS lm [36]. In contrast, the residual stress of the MPP CrN lm is lower than the PMS CrN lm because the ion energies of the majority of ions in the MPP plasma were comparable to those found in the dcMS plasma. The microstructure and residual stress differences of the CrN lms showed strong effects on the lm oxidation resistance. The intergra- nular fracture of the dcMS CrN lm is evident (Fig. 1A), which sug- gests a weak boundary bonding strength between the columnar grains. It is not surprising that the opened boundaries along the long columnar grains can be the diffusion paths for the outward diffu- sion of the Cr and N species and the inward diffusion of O. The crystal- line Cr 2 O 3 phase and a large amount of -Cr 2 N phase were detected in the dcMS CrN lm as early as 600 C. The c-CrN structure was only thermally stable up to 700 C (Fig. 2A). And the hardness of the dcMS CrN lm after annealing at 800 C maintained 43% of that of the as-deposited lm. The oxidation activation energy of the dcMS CrN lm obtained in the current study is about 116 kJ/mol. The PMS CrN lm showed the breaking down of the columnar grain growth with the development of ne granular grains but with a relatively high residual stress (4.5 GPa) (Fig. 1B). The ne grain size and higher residual stress of the PMS CrN lm led to a high as- deposited hardness of 28 GPa. However, the large amount of grain boundaries increases the intrinsic instability of the nano-structured state by the occurrence of grain growth at elevated temperatures. They can also act as outward diffusion paths for N atoms from a ther- modynamic point of view. The higher residual stress of the PMS CrN lm also results in an intrinsic instability of the microstructure of the lms at elevated temperatures because of the lower thermal acti- vation needed to start recovery in such structures [15]. Consequently, the PMS CrN lm exhibited a similar oxidation behavior to that of the dcMS CrN lm. The crystalline Cr 2 O 3 phase and a large amount of - Cr 2 N phase were detected in the PMS CrN lm at 700 C. The c-CrN structure was thermally stable up to 800 C (Fig. 2B). And the hard- ness of the PMS CrN lm after annealing at 800 C was 45% of the as-deposited lm. The oxidation activation energy of the PMS CrN lm obtained in the current study is about 141 kJ/mol. Fig. 8. (A) The parabolic oxidation kinetics for the MPP CrN lms at the temperature range from 700 C to 900 C, and (B) Arrhenius plot of the dcMS, PMS and MPP CrN lms annealed at 600 C to 900 C in the ambient air. 3289 J. Lin et al. / Surface & Coatings Technology 206 (2012) 32833290 The dominant transgranular fracture of the MPP CrN lm suggests a strong boundary bonding strength between the grains (Fig. 1C), which is attributed to the dense microstructure. The residual stress of the MPP CrN lm is 2.5 GPa, which is comparable to that of the dcMS CrN lm but lower than that of the PMS CrN lm. The dense structure of the MPP CrN lm can effectively reduce the inward and outward diffusion rates of the ion species. Combined with the dense structure effect, the low residual stress in the MPP CrN lm probably slowed down the phase transformation from c-CrN to -Cr 2 N. As a re- sult, the MPP CrN lm exhibited superior oxidation resistance than the dcMS and PMS CrN lms. Only a small amount of crystalline Cr 2 O 3 and -Cr 2 N phases was detected in the MPP CrN lm at 700 C. The c-CrN structure was thermally stable up to 900 C (Fig. 2C). And the hardness of the MPP CrN lm after annealing at 800 C was 67% of that of the as-deposited lm. The MPP CrN lm exhibited an activation energy of 195 kJ/mol. It is considered that the higher oxidation activation energy value in the MPP CrN lm is because of the dense microstructure which hinders the diffusion of ion species through the grain boundaries. 5. Conclusions The oxidation behavior of the CrN lms deposited by dcMS, PMS and MPP techniques was studied in the temperature range of 600 to 1000 C. The as-deposited CrN lms exhibited a cubic structure and similar stoichiometry composition, but with different microstructures and residual stresses. It was found that the MPP CrN lm exhibited superior oxidation resistance as compared to the dcMS and PMS CrN lms. Only a small amount of crystalline Cr 2 O 3 and hexagonal -Cr 2 N phases was detected in the MPP CrN lm after 700 C. After annealing at 900 C, the MPP CrN lm exhibited an extremely dense structure with a strong cubic (311) peak. The MPP CrN lm main- tained 67% of the as-deposited hardness after annealing at 800 C. In contrast, the dcMS and PMS CrN lms exhibited a porous structure with a rapid degradation of the cubic phase after 700 C and 800 C, respectively. The results showed that all lms exhibited parabolic ox- idation behavior below 900 C. The oxidation activation energies for the dcMS, PMS and MPP CrN lms are 116 kJ/mol, 141 kJ/mol and 195 kJ/mol, respectively. The improved oxidation resistance of the MPP CrN lm is attributed to its dense microstructure and low resid- ual stress. Acknowledgments Support of this research program from the North American Die Casting Association (NADCA) and Department of Energy (DOE-OIT) is gratefully acknowledged. References [1] C. Paternoster, A. Fabrizi, R. Cecchini, M.E. Mehtedi, P. Choquet, J. Mater. Sci. 43 (2008) 3377. [2] P.H. Mayrhofer, H. Willmann, C. Mitterer, Surf. Coat. Technol. 146147 (2001) 222. [3] H. Ichimurah, A. Kawana, J. Mater. Res. 9 (1) (1994) 151. [4] I. Milosev, H.H. Strehblow, B. Navinsek, Surf. Coat. Technol. 7475 (1995) 897. [5] I. Miloev, J.M. Abels, H.-H. Strehblow, B. Navinek, M. MetikoHukovi, J. Vac. Sci. Technol., A 14 (4) (1996) 2527. [6] J. Lin, Z.L. Wu, X.H. Zhang, B. Mishra, J.J. Moore, W.D. Sproul, Thin Solid Films 517 (2009) 1887. [7] J. Lin, J.J. Moore, W.D. Sproul, B. Mishra, Z.L. Wu, J. Wang, Surf. Coat. Technol. 204 (2010) 2230. [8] G. Greczynski, J. Jensen, J. Bohlmark, L. Hultman, Surf. Coat. Technol. 205 (2010) 118. [9] J. Lin, B. Mishra, J.J. Moore, W.D. Sproul, Surf. Coat. Technol. 202 (2008) 3272. [10] M. Oden, J.D. Almer, G. Hakansson, Surf. Coat. Technol. 120121 (1999) 272. [11] E. Huber, S. Hofmann, Surf. Coat. Technol. 6869 (1994) 64. [12] P. Panjan, B. Navinsek, A. Cvelbar, A. Zalar, I. Milosev, Thin Solid Films 281282 (1996) 298. [13] M.-A. Djouadi, C. Nouveau, O. Banakh, R. Sanjins, F. Lvy, G. Nouet, Surf. Coat. Technol. 151152 (2002) 510. [14] S. Veprek, M. Jilek, Pure Appl. Chem. 74 (3) (2002) 475. [15] C. Mitterer, P.H. Mayrhofer, J. Musil, Vacuum 71 (2003) 279. [16] P.H. Mayrhofer, C. Mitterer, Surf. Coat. Technol. 133 (2000) 131. [17] V. Kouznetsov, K. Mack, J.M. Schneider, U. Helmersson, I. Petrov, Surf. Coat. Technol. 122 (1999) 290. [18] I.K. Fetisov, A.A. Filippov, G.V. Khodachenko, D.V. Mozgrin, A.A. Pisarev, Vacuum 53 (1999) 133. [19] K. Mack, V. Kouznetsov, J. Schneider, U. Helmersson, I. Petrov, J. Vac. Sci. Technol., A 18 (4) (2000) 1533. [20] U. Helmersson, M. Lattemann, J. Bohlmark, A.P. Ehiasarian, J.T. Gudmundsson, Thin Solid Films 513 (2006) 1. [21] R. Chistyakov, B. Abraham, W.D. Sproul, Proceedings of the 49th Annual SVC Technical Conference, Washington, DC, , April 2327 2006, p. 88. [22] W.D. Sproul, R. Chistyakov, B. Abraham, Bull. Soc. Vac. Coaters (Summer 2006) 35. [23] J. Lin, W.D. Sproul, J.J. Moore, S.L. Lee, Z.L. Wu, R. Chistyakov, B. Abraham, JOM 63 (6) (2011) 48. [24] J. Lin, J.J. Moore, W.D. Sproul, B. Mishra, J.A. Rees, Z. Wu, R. Chistyakov, B. Abraham, Surf. Coat. Technol. 203 (2009) 3676. [25] M. Lattemann, U. Helmersson, J.E. Greene, Thin Solid Films 518 (2010) 5978. [26] A.P. Ehiasarian, P.Eh. Horsepian, L. Hultman, U. Helmersson, Thin Solid Films 457 (2004) 270. [27] J. Lin, W.D. Sproul, J.J. Moore, S.L. Lee, S. Myers, Surf. Coat. Technol. 205 (2011) 3226. [28] J. Lin, W.D. Sproul, J.J. Moore, J. Vac. Sci. Technol., A 29 (6) (2011) 061301. [29] R.J.D. Tilley, John Wiley & Sons Ltd, Chichester, West Sussex, England, September 20, 2004, p. 302. [30] A. Patterson, Phys. Rev. 56 (10) (1939) 978. [31] H.-Y. Chen, F.-H. Lu, J. Mater. Sci. Lett. 22 (2003) 817. [32] Y. Otani, S. Hofmann, Thin Solid Films 287 (1996) 188. [33] D.B. Lee, Y.C. Lee, S.C. Kwon, Surf. Coat. Technol. 141 (2001) 227. [34] P. Panjan, B. Navinsek, A. Cvelbar, A. Zalar, I. Milosev, Thin Solid Films 281 (1996) 298. [35] H. Ichimura, A. Kawana, J. Mater. Res. 9 (1994) 151. [36] J. Lin, J.J. Moore, B. Mishra, M. Pinkas, W.D. Sproul, J.A. Rees, Surf. Coat. Technol. 202 (2008) 1418. 3290 J. Lin et al. / Surface & Coatings Technology 206 (2012) 32833290