# Structural and Mechanical Properties of CrNx Coatings Deposited by Medium-Frequency Magnetron Sputtering with and without Ion Source Assistance

Authors: Can Xin Tian; Bing Yang; Jun He; Hong Jun Wang; De Jun Fu
Journal: Journal of Nanomaterials
 (2011)

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## Abstract

CrNx coatings were deposited on Si (100) and WC-Co substrates by a home-made medium-frequency magnetron sputtering system with and without thermal filament ion source assistance. The structure and composition of the coatings were characterized by X-ray diffraction, atomic force microscopy, scanning electron microscopy, and transmission electron microscopy. The mechanical and tribological properties were assessed by microhardness and pin-on-disc testing. The ion source-assisted system showed a deposition rate of 3.88 μm/h, much higher than the value 2.2 μm/h without ion source assistance. The CrNx coatings prepared with ion source assistance exhibited an increase in microhardness (up to 16.3 GPa) and adecrease in friction coefficient (down to 0.48) at the optimized cathode source-to-substrate distance.


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## Body

## 1. Introduction

Transition metal nitrides, especially chromium nitride (CrN), have been studied extensively due to their unique properties, including high hardness, good wear resistance, as well as excellent corrosion and high-temperature oxidation resistance [1–4]. They are widely applied in industry as protective coatings [5–7]. Recent studies also revealed magnetic properties in CrN, and it might find applications in the electronic industries [8, 9]. Many methods have been used for the deposition of CrN films, among which unbalanced magnetron sputtering produces good quality samples at high-deposition rates [2]. The pulsed DC reactive magnetron sputtering technique was characterized by improved ionization and a high ion-to-neutral particle ratio during deposition to enhance the quality of coatings [10], but more importantly it increased the kinetic energy of the ions in the plasma, which can enhance the ion bombardment of the substrate and film [11–14]. Therefore, high-quality CrN coatings have been prepared by pulsed dc magnetron sputtering [15, 16], and the high-power pulsed magnetron sputtering has also been developed for deposition of CrN coatings [17, 18]. It is known that low ionization efficiency in the plasma is a hurdle of magnetron sputtering; therefore, plasma or ion sources have been developed to improve ionization efficiency [19, 20]. In particular, Wei et al. reported dense and thick films of transition metal nitrides, including ZrN and TiN, by means of plasma-enhanced magnetron sputtering, where an electron source of thermal filament type is a key technology [21, 22]. In order to prepare thick protective coatings with high deposition rate, high microhardness, and ideal surface chemistry, it is necessary to introduce high-density plasma in pulsed dc magnetron sputtering systems.In this paper, we have prepared CrNx coatings at various magnetron cathode source-substrate distances by medium-frequency (40 kHz) magnetron sputtering with a thermal filament ion source and conducted characterization in comparison with samples prepared without the use of the ion source. We intended to find out the influence of cathode source-to-substrate distances and ion source on the deposition rate, microstructural, mechanical, and tribological properties. Then, we have optimized the source-substrate distance at which the ion source best assists the deposition process, producing CrNx coatings with superior properties.


## 2. Experiment Details

The CrNx coatings were deposited by using a modified closed field twin unbalanced magnetron sputtering system. The vacuum chamber is ϕ400×500 mm in dimension. The ion source was powered by a supply of 20 A and 24 V and was mounted in the middle-upper area of the chamber. Cr sheets with a purity of 99.99% and an area of 10×40 cm2 were used as a cathode source material. Prior to deposition, a base pressure was less than 5×10-3Pa. For substrates, p-type Si (100) and mirror-polished WC-Co plates were ultrasonically cleaned in acetone and methanol, rinsed in de-ionized water, and dried in N2 before being loaded into the deposition chamber. Then, they were ion etched for 30 min in Ar atmosphere at a pressure of 2.0 Pa and a negative bias voltage of 800 V applied to the substrate holder. N2 (99.99%) and Ar (99.99%) were used as working gases. First, a layer of pure Cr (about 230 nm) was deposited onto the substrate for 5 min in Ar ambient at 0.25 Pa and −100 V to improve the adhesion. Then, N2 was let in, and Ar flow rate was tuned to keep an Ar : N2 ratio of 1 : 1. The total pressure was kept at 0.25 Pa, and the substrate bias was fixed at −100 V. The medium-frequency power used was 7.0kW, and cathode source-substrate distance was varied between 50 and 140 mm. The substrates temperature was kept at 150°C. The ion source was a tungsten filament which emitted electrons when heated by a high current and could produce ions of argon gas fed to the outlet of the filament source. The ion source was installed at the upper part of the chamber, similar to the configuration described in the literature [23].The crystal structure of the deposited CrNx coatings was characterized by X-ray diffraction (XRD, Bruker-Axs D8 advanced which was operated at voltage and current of 40 kV and 40 mA, resp.) with a Cu ka radiation and JEOL JEM 2010 transmission electron microscopy (TEM). The deposition rate was evaluated from the thickness of the films measured with a FTSS2-S4L-3D step profiler. The cross-section micrographs were measured using Sirion FEG scanning electron microscopy (SEM), and the composition of CrNx coatings was determined by using an EDAX genesis 7000 energy dispersive spectroscopy (EDS) system operated at 12 kV. The surface topography was analyzed using an atomic force microscope (AFM) (Shimadzu SPM-9500J3) operated in the tapping mode. The hardness was measured using an HX-1000 microhardness tester with a load of 25 g (the indentation depth was about 250 nm) and taking the average of 5 values. The friction and wear measurements of the CrNx coatings were carried out by using an MS-T3000 ball-on-disk tester which slides in ambient air at 30°C, at relative humidity of 70%, with a Si3N4 ball of 3 mm in diameter being used as the mating material, on which a 4 N load was applied. The average sliding speed was 0.02 m/s for a fixed sliding time of 30 min, and the friction coefficients were recorded during the test.


## 3.  Results and Discussion

Figure1 shows the XRD spectra of CrNx coatings deposited under various source-substrate distances, dss. The CrNx coatings contain two phases of fcc CrN and hexangular Cr2N, their corresponding PDF numbers being 65-2899 and 79-2159, respectively. Only the CrN (200) peak is observed for the coating deposited atdss=90mm. With increasing dss, the XRD data show the structure of the CrNx coatings to be changed from CrN to a mixture of Cr2N + CrN. At the lower extreme, dss=50 mm, the planes of Cr2N (002), together with CrN (200) and (111), can be seen whereas at larger distance of 140 mm, the films deposited exhibit inconspicuous overlap of Cr2N (002) and CrN (200) orientations.Figure 1
XRD patterns of CrNx coatings deposited at various dss.The energies of the depositing particles were different at differentdss because of the collision of ions (N, Ar, and Cr). The particles bombarded the substrate and heat the substrate. The ratio of ion to neutral particles (Ar, N, and Cr) arriving at the growing film would be different at different dss. These factors influence the film growth kinetics, which finally determine the orientation and phase structure of the CrNx coatings. The broadening of the diffraction peaks of CrNx coatings is related to the changes in the grain size, thickness, and residual stress in the coating. The different ratio of N/Ar has an influence on the composition of CrN or Cr2N [24]. Therefore, the formation of CrN or Cr2N at different dss is attributed to the different N/Ar ratio influenced by dss.Also shown in Figure1 is the influence of the hot filament ion source; CrNx coatings deposited with ion source assistance have different diffraction peaks at all values of dss. In particular, at dss of 90 mm, the intensity of (200) peak is enhanced. The slightly higher intensity of the XRD peaks in the CrN coatings deposited with the ion source assistance can be related to the enhanced ion bombardment from the plasma, which may lead to a higher substrate temperature as well as a higher ion-to-neutral particle ratio.Figure2(a) shows bright-field TEM images of CrNx coatings deposited without ion source assistance, which reveals nonuniform CrNx grains. The corresponding selected area diffraction pattern reveals obvious CrN and blurry Cr2N phases. On the contrary, with the use of ion source Figure 2(b), uniform CrNx grains are observed and selected area diffraction shows obvious diffraction rings of CrN and Cr2N, revealing the polycrystalline nature of the film, with diffraction points attributed to the Si (100) substrate. The uniform CrNx grains with distinct grain boundaries suggest higher microhardness of the corresponding coatings.Bright-field TEM images and selected area diffraction of CrNx coatings deposited at dss = 90 mm. The view directions are normal to the coating surface. (a) Samples prepared without ion source assistance, (b) with ion source assistance.
(a)(b)Figure3 shows the deposition rate of the CrNx coatings as a function of dss. As a general tendency, the deposition rate of the coatings decreases with increasing dss. The deposition rate is further increased at dss values of 90 mm and 140 mm with the assistance of the ion source. At dss=50mm, however, the ion source assistance tends to decrease the deposition rate.Figure 3
Deposition rate as a function of thedss of the CrNx coatings.At larger source-substrate spacing, the sputter-produced particles arriving at the substrate decrease in number due to the collision of Cr and N atoms with the plasma of N2, Ar, N+, Ar+, and secondary electrons. However, with the use of thermal filament ion source, more ions, especially Ar ions, were generated, which bombarded the Cr target and produced more Cr particles [3, 25]. As a result, the deposition rate is higher than that without ion source assistance. At close source-substrate spacing (dss=50mm), with thermal filament ion source assistance, the increased amount of Ar and other ions causes severe re sputtering of the film surface. Therefore, the deposition rate becomes lower than that without ion source assistance. With the increase of dss, the energies of deposition particles decreased because of the collision in the plasma, especially at dss much larger than molecular mean-free-path. Hence, the deposition rate at larger dss with the ion source assistance becomes larger than without ion source assistance.Figure4 shows typical three-dimensional AFM morphologies taken from the CrNx coatings deposited at dss of 50, 90, and 140mm without and with thermal filament ion source assistance. The topographies shown in Figure 4(a) suggest that the CrNx coatings deposited at 50 mm are composed of columns with irregular tops. When the source-substrate spacing increases to 90 mm, the size of the extrusive tops was significantly reduced (Figure 4(b)). At even larger dss, the extrusive tops become more regular and an even smoother surface is observed (Figure 4(c)). Figure 5 shows the root-mean-square (RMS) roughness calculated from the AFM images of the CrNx coatings deposited at various dss without and with thermal filament ion source assistance. Corresponding to the AFM observations in Figure 4, the RMS roughness of the CrNx coatings deposited at 50 mm was relatively large at shorter source-substrate distance. The use of thermal filament ion source gives rise to the reduction of RMS roughness from 10.3 to 8.6 nm at dss=50mm. At larger source-substrate distance, the difference becomes negligible.AFM morphologies of CrNx coatings deposited at dss of 50 mm (a), 90 mm (b), and 140 mm (c). The images on the left-hand side are of samples prepared without ion source, and those on the right-hand side are of samples prepared with ion source assistance.
(a)(b)(c)Figure 5
Variation in rms roughness measured from AFM images of the CrNx coatings as a function of dss.When the source-substrate spacing is small, the deposition rate is high (Figure3) and the growth is columnar, which gives a large roughness. More energetic ions bombard the substrate, which affected the nucleation kinetics [26], resulting in rapid growth of the grain, thereby exhibiting larger particle sizes. With increasing dss, frequent collision reduces the kinetic energies of particles reaching the surface, and the deposition is slowed down, leading to uniform surfaces with extrusions of smaller particle size and higher density.Figure6 shows cross-section SEM images of the CrNx coatings deposited without and with ion source assistance at dss of 90 mm. One sees a columnar growth throughout the whole film thickness without the ion source assistance. In the process of using ion source, columnar growth is not obvious and the coating becomes denser, apparently resulting from the energetic bombardment by ions produced with the ion source assistance.Cross-sectional SEM image of CrNx coatings deposited at dss = 90 mm (a) without and (b) with ion source assistance.
(a)(b)Figure7 shows the microhardness of the CrNx coatings as a function of source-substrate distance, which exhibits the same trend, but the values are higher when ion source assistance is applied during deposition. At dss=90 mm, the highest hardness is observed. This is accounted for by better crystallization and higher N concentration (measured by EDS) measured from the samples. The CrNx coating deposited with the thermal filament ion source had higher N concentration (as shown in Figure 8), and the films were denser, with much finer grains (as shown Figure 2). It is believed that the grain size rather than the existence of Cr2N phase influences the hardness values [27], which explains the further improvement of the microhardness at dss = 90 mm.Figure 7
Variation of microhardness of CrNx coatings as a function of dss.The EDS images of CrNx coatings deposited at Dts = 90 mm. (a) Samples without ion source assistance, N/Cr = 0.9075; (b) with ion source assistance, N/Cr = 0.9242.
(a)(b)Figure9 shows the friction coefficients of CrNx coatings. The average friction coefficient of the CrNx films prepared without ion source is 0.53 and is decreased to 0.48 with ion source assistance. This is consistent with the enhanced microhardness and the reduction in the surface roughness of the CrNx coatings.Figure 9
Variation of friction coefficient with sliding time of CrNx coatings at dss = 90 mm.


## 4.  Conclusion

We have prepared CrNx coatings by medium-frequency magnetron sputtering and demonstrated the improvement of the structural and mechanical properties of coatings by introducing thermal filament ion source during deposition. The CrNx coatings deposited with ion source assistance exhibited an increase in microhardness from 13.25–16.3 GPa at a source-substrate distance of 50 mm and from 16.0-17.0 GPa at the optimized dss of 90 mm. The friction coefficient was decreased typically from 0.53–0.48. A deposition rate of 3.88 μm/h was achieved, and the roughness was 6.0 nm for the coatings deposited at dss of 90 mm. The results show that the use of simple ion source assistance may be promising for high-rate deposition of CrNx coatings.



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*Source: 534647-2010-09-05.xml*