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Nuclear Instruments and Methods in Physics Research B 269 (2011) 1058–1062

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Nuclear Instruments and Methods in Physics Research B
journal homepage: www.elsevier.com/locate/nimb

Deposition of tungsten nitride on stainless steel substrates using plasma focus device
G.R. Etaati a,b,⇑, M.T. Hosseinnejad a, M. Ghoranneviss a, M. Habibi a, M. shirazi c
a

Plasma Physics Research Center, Science and Research Branch, Islamic Azad University, Tehran, Iran Nuclear Engineering and Physics Department, Amirkabir University of Technology, 424 Hafez Ave., Tehran, P.O. Box 015875-4413, Iran c Physics Department, Faculty of Science, Arak University, Arak, Iran
b

a r t i c l e

i n f o

a b s t r a c t
Tungsten nitride (WN) films were deposited on the stainless steel-304 substrate by a 2 kJ Mather-type plasma focus device. The preparation method and characterization data are presented. X-ray diffractometer (XRD), scanning electron microscopy (SEM) and atomic force microscopy (AFM) were employed for the characterization of the samples obtained with different number of focus shots, respectively. The average size of crystallites (from XRD), sub-micro-structures (from SEM) and particles (from AFM images) increase when the number of shots increase from 10 to 20 then 30, then they decrease when the substrate is exposed to 40 shots. Ó 2011 Elsevier B.V. All rights reserved.

Article history: Received 1 January 2011 Received in revised form 11 February 2011 Available online 1 March 2011 Keywords: Plasma focus device Tungsten nitride Thin film XRD SEM AFM

1. Introduction Transition metal nitrides are extensively used in various scientific and industrial applications, due to their substantial hardness [1], chemical stability [2], desirable electrical conductivity and high melting point. Especially, they are widely used in various engineering applications such as machining applications (e.g. cutting tools), aeronautics (e.g. turbine blades), automotives (e.g. engine parts [3]) and microelectronics (diffusion barriers in semiconductor technology [4,5]). During the recent decades, various deposition techniques have been investigated for production of transition metal nitride thin films [6–10]. In a number of works, tungsten nitride has been employed for hard coating [11–13] and electrical and optical properties and the composition of tungsten nitride thin films have been examined on Silicon wafers [14]. In addition, tungsten nitride thin films have desirable mechanical characteristics (high adhesion and hardness) and tribological properties (e.g. high wear resistance) [15,16] and due to these properties, various methods have been tried for deposition of tungsten nitride [17–21]. In recent decades, the dense plasma focus (DPF) device [22,23] has been employed for many applications such as generation of
⇑ Corresponding author at: Nuclear Engineering and Physics Department, Amirkabir University of Technology, 424 Hafez Ave., P.O. Box 015875-4413, Tehran 015875-4413, Iran. Tel.: +98 21 44869627; fax: +98 21 44869626. E-mail addresses: r_etaati@aut.ac.ir, etaati.reza@gmail.com (G.R. Etaati).
0168-583X/$ - see front matter Ó 2011 Elsevier B.V. All rights reserved. doi:10.1016/j.nimb.2011.02.083

energetic ions, neutrons, X-rays and relativistic electrons [24] and deposition of thin films [25–27]. The use of plasma focus device for film deposition purposes has shown that this device possesses attractive features such as high deposition rates, energetic deposition, no need to heat substrates and possible film deposition under a reactive background gas pressure. Recently, this device has been used efficiently for the deposition of thin films [25–27]. Hussain et al. [25] have successfully deposited thin films of TiN on silicon wafers using a low energy DPF. Soh et al. [26] studied the dynamics of carbon ablation plasma by shadow-graphic studies of DLC, using a 3.3 kJ Mather-type DPF device. They reported that the films deposited at different angular positions with respect to anode axis exhibit different physical properties. Rawat et al. [27] investigated the deposition of Fe thin films by moving exposed samples from center to offcenter, which was proved to be effective in forming more uniform surface. In the present work, for the first time, we have deposited tungsten nitride thin films on the stainless steel 304 substrates, using a low energy (2 kJ) plasma focus device. We have investigated the effects of different number of focus shots at two different angular positions with respect to anode axis (0° and 30°). In each shot, the substrates were kept at 80 mm away from the tungsten material on the tip of anode. A thin film of tungsten nitride was deposited on the substrate due to the interaction of the ablated tungsten ions with reactive nitrogen ions. The studies on the structural and morphological properties of deposited films were undertaken.

As a result. This phenomenon can be explained by noticing that for the samples treated by 10. Another observation from Fig. a Pyrex glass insulator with 20. Thus the deposited film contains some tungsten atoms. react with the nitrogen ions released in each shot. XRD Results Fig. 30 and 40) with the same axial position of the samples (80 mm away from the anode tip) but at two different angles with respect to the anode axis (0° and 30°). A mobile shutter is located between the anode and the samples. not only the relative locations of the peaks. we evidence a decrease in the above mentioned quantity. deposited on the substrate. In addition.. Part of these tungsten atoms. 20. The first effect is the release of substantial amount of energy which causes a rapid rise in the temperature of samples.5 mm inner diameter and 2. but also their relative intensities are highly consistent with JCPDS. . we have analyzed the structural properties of all deposited films in terms of angular position and the number of fired focus shots. we observe that at 0° angular position. The formation process of DPF has different phases as described follows: Charging the electrodes by a high voltage causes a low inductance gas breakdown around the insulator sleeve. The desirable focusing is indicated by an intense voltage peak in the voltage probe signal that is recorded by a four-channel TDS 2014B (100 MHz) TEKTRONIX digital oscilloscope. The second effect is caused by collision of the accelerated electrons with the tungsten substance on the top of the anode. The cathodic rods and focus chamber are both connected to the ground potential. To separate the electrodes and facilitate the formation of current sheaths between them. Also the total inductance of the system is about 90 nH and discharge current is about 170 kA. Thus. high temperature and high density of the plasma cause a rapid change in its inductance which in turn results in inducing electric fields with very high intensity. Furthermore. Using X-ray diffraction (XRD) spectra. the shutter is removed and deposition is started.5 mm thickness is used which covers 35 mm of the anode length. we specifically studied the micro-structure and surface morphology of the films using scanning electron microscopy (SEM) images and atomic force microscopy (AFM). A schematic diagram of the DPF device used in our experiments. The electrodes are placed in a stainless steel focus chamber which is vacuumed up to 10À3 Torr by a rotary vane pump then filled with high purity nitrogen up to an optimum pressure 1 Torr. 3. 10 lF) and the experiment is done at room temperature. Etaati et al. a rich content of tungsten nitride is eventually deposited on the film. first using alcohol for a period of 5 min. For 40 focus shots. The results show that for both angular positions. the copper anode is of 160 mm length and 20 mm diameter. 1. it collapses radially inward during the final focus phase. Then they are axially mounted on the sample holder with a distance of 80 mm from the anode tip. The strong electric field accelerates the electrons and ions in opposite directions (i. triggering some tungsten ions to ablate. which altogether form the cathode. respectively [28]. For the film deposited with 30 focus shot at 0° angular position. In the electrode system.: 00-004-0806 and JCPDS Card No. The relative locations of all W and WN diffraction peaks are consistent with Joint Committee for Powder Diffraction Standards (JCPDS) standard data for W and WN powders (JCPDS Card No. Experimental details and methodology A schematic diagram of the dense plasma focus (DPF) system used in our experiments is shown in Fig. diffraction peaks of WN (3 1 1) and WN (2 2 0) crystalline planes also appear in the XRD patterns.1. After achieving a sharp focus. From Fig. each with 150 mm length and 12 mm diameter. and form tungsten nitride which is deposited on the substrate. When this current sheath reaches the top of electrode assembly. In this experiment. The DPF used in our experiments is of Mather-type which is powered by a single capacitor (20 kV. 1. towards the anode and towards the top of the chamber). surrounded by 12 equidistance copper rods. Our experiments involved multiple focus shots (10. 2(a). and filled with tungsten. Our observations in terms of various crystalline planes (appeared as diffraction peaks in the images) are listed in Table 1.G. For tungsten nitride deposition. react with the accelerated nitrogen ions in the next shots through the ion implantation process. Furthermore. 2(a) is that for the samples positioned at 0° angle. / Nuclear Instruments and Methods in Physics Research B 269 (2011) 1058–1062 1059 2. The DPF system is employed as a source of high-energy nitrogen ions which react with the tungsten ions ablated from the anode tip. 2 shows the XRD patterns of an unexposed film compared to the patterns of the films deposited with various focus shots at 0° and 30° angular positions and all 80 mm away from the anode tip. some of the tungsten plasma still does not react with generated nitrogen ions and atoms in each shot. the WN crystalline layers deposited on stainless steel-304 substrates grow as they are exposed to more focus shots. 20 and 30 focus Fig. a hole with 7 mm depth and 19 mm diameter has been devised into the tip of the anode. The short lifetime. the collision results in etching and cleans the substrate surface in prior to the deposition process. This is while for 30 and 40 focus deposition shots. however.: 00-075-1012). 20 and 30 shots are applied. Results and discussion 3. the stainless steel substrates are 10 Â 10 Â 1 mm3 in size. Collision of the accelerated ions with the samples causes two effects. then with acetone for 10 min. the intensity of WN diffraction peaks increases with the number of focus shots when 10. These extra diffraction peaks of WN crystalline planes are the results of the proper phase induction caused by the additional focus shots. a current sheath is formed and accelerated axially up the chamber by the J Â B force. They are ultrasonically cleaned.R.e. exposition to 10 and 20 focus deposition shots results in substrate diffraction peaks as well as diffraction peaks of only WN (1 1 1) and WN (2 0 0) crystalline planes.

1060 G. 2. numbers of focus shots at 0°. increasing the number of shots to 40 is observed to decrease the average crystallite size. the film surface is significantly melted (due to high-energy ions in each shot) and rapidly cooled down afterwards.93 is Scherer constant. 3. 3 we observe that at a 0° angular position. further increase in the number of focus shots may cause partial amorphization of the deposited crystallite film. Thus. 3). A possible explanation is that too many focus shots cause increasing radiation damage due to excessive bombardment of the sample surface with high-energy ions. FWHM is the full width at half maximum (in radians) and h is Bragg’s angle of the diffraction peak. 3(d) shows that when the sample is treated with 40 shots. However. the energy and flux of the ions are smaller. in each focus shot. 2(b) show that at 30° angular position. XRD patterns of the films deposited for 10. all the tungsten ablated from the anode tip over the deposition region has not been transited to the WN phase. hence. This can be due to more frequent occurrence of transient annealing of the surface of treated samples with more focus shots. those intensities are considerably smaller than similar diffraction peaks in Fig. is deposited on the substrate. Noticeably. According to Sagar et al. In Fig. 30 and 40 focus deposition shots at (a) 0° and (b) 30° angular positions.3. From Fig. at 30° angular position (compared to 0°). Number of focus shots Crystallite size (nm) Relative intensity (a.2. 3. we have analyzed the surface morphology of the films Crystallite size ¼ kk ðFWHMÞ cos h ð 1Þ where k = 0.u. For various Table 1 Various crystalline planes for deposited thin films with different number of focus deposition shots at different angular positions. This is consistent with the increasing followed by decreasing of the average crystallite sizes that we observed in the XRD patterns. 20. As the number of focus shots increases from 10 to 20 then 30. 2(a). increasing numbers of focus shots only cause the appearance of diffraction peaks of WN (1 1 1) and WN (2 0 0) crystallite planes with increasing intensities. / Nuclear Instruments and Methods in Physics Research B 269 (2011) 1058–1062 Fig.54 A° is the wavelength of the source X-ray. with increasing the number of focus shots from 10 to 30 shots. the radiated ions are scattered in a small solid angle around the anode axis with an anisotropic distribution. less material with less energy is deposited on the substrate. [30] have shown that in plasma focus. In each experiment. [29]. Same possible explanation applies here: with 40 focus shots.272 206. 3.85 30 Shots 96. The impact of maximum energy ions on the surface of the films is an extra cause for the appearance of surface defects such as pits and craters in these films. AFM results Using the images acquired by an atomic force microscope (AFM).R. 2(a) shows that at 0° angular position. the estimated average crystallite sizes and relative intensities of typical diffraction peaks of the WN (1 1 1) crystalline plane have been recorded and are presented in Table 2. the average crystallite size grows as well. This undesirable process of rapid melting followed by fast cool-down also causes brittleness of the samples as well as graduate appearance of cracks and fissures on surface of the thin films (see Fig. The XRD spectra shown in Fig. Etaati et al. some tungsten which is still unreacted with the generated nitrogen. 3. shots.16 . k = 1. This is the main reason why no specific and uniform pattern can be observed in the crystallite structures formed on the surface of the films shown in Fig. 2(a and b).303 157. Fig.895 53. and at larger angles with respect to the anode axis.15 20 Shots 21. reducing the degree of crystallinity of the WN deposited film.) 10 Shots 18. consistent with the results shown in Figs. excessive bombardment of the sample surface with high-energy ions causes greater radiation damage and reduction of the size of sub-micro-structures on the surface of the film. Number of shots Angular position of substrates (°) Crystalline planes WN 111 p p p p p p p 200 p p p p p p p p 220 311 W 011 p p p p p p p p p 112 10 20 30 40 0 30 0 30 0 30 0 30 Table 2 Crystallite size and relative intensity calculated for diffraction peak of (1 1 1)WN crystalline plane for deposited thin films with different number of focus deposition shots at 0° angular position. 2(a).013 44. SEM results The SEM micrographs of samples exposed to 10–40 shots at 0° angular position are presented in Figs. Hence. 3(a–c)). the sub-micro crystalline structures formed on the film surface grow in size (see Fig. the thickness of the crystallite phase of tungsten nitride grows with the number of focus shots. We have estimated the average crystallite size using Scherer formula [31]. It is important to note that the reduction of diffraction peak intensities of substrate with increasing number of focus shots shows a growth in the coating deposited on the substrate surface. Fig. Bertalot et al. the size of sub-micro crystalline structures reduces as compared the case with 30 focus shots. However.24 40 Shots 39. the intensity of the diffraction peak for the W (0 1 1) crystallite plane increases with the number of focus shots which shows a growth in Tungsten crystalline.

5. AFM micrographs of samples exposed to (a) 10 shots. To analyze and compare the surface roughness of the deposited films. Comparison of the AFM images shown in Fig. Variations of the rms and average roughness of the film surface in terms of the number of focus shots for thin films deposited at 0° angular position. (c) 30 shots and (d) 40 shots at 0° angular position. and their energy and flux varies with their angle relative to the anode axis [30]. (b) 20 shots. The rationale behind this is that. 3. using critical dimension analysis of the AFM images. Number of focus shots Diameter (nm) 10 Shots 80–230 20 Shots 120–340 30 Shots 200–650 40 Shots 160–390 in each experiment. (b) 20 shots. All the images have been obtained with a scanning area of 5 lm  5 lm.R. Table 3 The range of the diameter of particles obtained from critical dimension analysis of AFM images for deposited thin films with different number of focus deposition shots at 0° angular position. (c) 30 shots and (d) 40 shots at 0° angular position. . For each number of focus shots. the particles have smaller sizes and are distributed more homogenously. 4 reveals that in case of the smallest number of focus shots (10 shots). however. different areas of the film surface are expected deposited with various numbers of focus shots at 0° angular position.G. the energy flux of the ions is so high that radiation damage reduces the size of the particles. as it was previously mentioned. SEM micrographs of samples exposed to (a) 10 shots. This growth in particle size is caused by the increased strength of the annealing of deposited layer with more focus shots. Thus. in plasma focus the ions are radiated in a fountain-like structure. 4. With 40 focus shots. Fig. Etaati et al. with 40 shots. we have estimated the range of diameter of particles. Fig. the size of the deposited particles gets smaller than the particles deposited with 30 focus shots. As it was previously mentioned. The 2D surface topography of the deposited films is shown in Fig. The results are listed in Table 3 and show an increase in the size of the deposited particles when the number of focus shots is increased from 10 to 20 then 30 shots. 4. we measured the roughness of three random areas over the surface of the deposited film and recorded the average and root mean square (rms) values of the measurements. / Nuclear Instruments and Methods in Physics Research B 269 (2011) 1058–1062 1061 Fig.

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